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

Lehmann, C. S.; Picón, A.; Bostedt, C.

The availability at x-ray free electron lasers of generating two intense, femtosecond x-ray pulses with controlled time delay opens the possibility of performing time-resolved experiments for x-ray induced phenomena. We have applied this capability to molecular dynamics. In diatomic molecules composed of low-Z elements, K-shell ionization creates a core-hole state in which the main decay is an Auger process involving two electrons in the valence shell. After Auger decay, the nuclear wavepackets of the transient two-valence-hole states continue evolving on the femtosecond timescale, leading either to separated atomic ions or long-lived quasi-bound states. By using an x-ray pump and anmore » x-ray probe pulse tuned above the K-shell ionization threshold of the nitrogen molecule, we are able to observe ion dissociation in progress by measuring the time-dependent kinetic energy releases of different breakup channels. We simulated the measurements on N2 with a molecular dynamics model that accounts for K-shell ionization, Auger decay, and time evolution of the nuclear wavepackets. In addition to explaining the time-dependent feature in the measured kinetic energy release distributions from the dissociative states, the simulation also reveals the contributions of quasi-bound states.« less

Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy

DOE PAGES

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.; ...

2016-12-21

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

First and second energy derivative analyses for open-shell self-consistent field wavefunctions

NASA Astrophysics Data System (ADS)

Yamaguchi, Yukio; Schaefer, Henry F., III; Frenking, Gernot

A study of first and second derivatives of the orbital, electronic, nuclear and total energies for the self-consistent field (SCF) wavefunction has been applied to general open-shell SCF systems. The diagonal elements of the Lagrangian matrix for the general open-shell SCF wavefunction are adapted as the 'oŕbital' energies. The first and second derivatives of the orbital energies in terms of the normal coordinates are determined via the finite difference method, while those of the electronic, nuclear and total energies are obtained by analytical techniques. Using three low lying states of the CH2 and H2CO molecules as examples, it is demonstrated that the derivatives of the SCF energetic quantities with respect to the normal coordinates provide useful chemical information concerning the respective molecular structures and reactivities. The conventional concept of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) has been extended to the molecular vibrational motion, and the terminology of vibrationally active MOs (va-MOs), va-HOMO and va-LUMO has been introduced for each normal coordinate. The energy derivative analysis method may be used as a powerful semi-quantitative modelin understanding and interpreting various chemical phenomena.

Experimental and theoretical study of the B(2)2Σ+ → X(1)2Σ+ system in the KSr molecule

NASA Astrophysics Data System (ADS)

Szczepkowski, Jacek; Grochola, Anna; Kowalczyk, Paweł; Dulieu, Olivier; Guérout, Romain; Żuchowski, Piotr S.; Jastrzebski, Włodzimierz

2018-05-01

Spectral bands for the B(2)2Σ+ → X(1)2Σ+ electronic transition in the doubly-polar open-shell KSr molecule are recorded at moderate resolution using the thermoluminescence technique. The spectra are simulated using three kinds of advanced electronic structure calculations, allowing for an assessment of their accuracy on one hand, and for the derivation of fundamental spectroscopic constants of the X(1)2Σ+ KSr ground state and the excited electronic state B(2)2Σ+ , on the other hand. These results should facilitate further studies aiming at creating ultracold bosonic or fermionic KSr molecules.

Rotational and fine structure of open-shell molecules in nearly degenerate electronic states

NASA Astrophysics Data System (ADS)

Liu, Jinjun

2018-03-01

An effective Hamiltonian without symmetry restriction has been developed to model the rotational and fine structure of two nearly degenerate electronic states of an open-shell molecule. In addition to the rotational Hamiltonian for an asymmetric top, this spectroscopic model includes the energy separation between the two states due to difference potential and zero-point energy difference, as well as the spin-orbit (SO), Coriolis, and electron spin-molecular rotation (SR) interactions. Hamiltonian matrices are computed using orbitally and fully symmetrized case (a) and case (b) basis sets. Intensity formulae and selection rules for rotational transitions between a pair of nearly degenerate states and a nondegenerate state have also been derived using all four basis sets. It is demonstrated using real examples of free radicals that the fine structure of a single electronic state can be simulated with either a SR tensor or a combination of SO and Coriolis constants. The related molecular constants can be determined precisely only when all interacting levels are simulated simultaneously. The present study suggests that analysis of rotational and fine structure can provide quantitative insights into vibronic interactions and related effects.

Potential energy curves of the Na2+ molecular ion from all-electron ab initio relativistic calculations

NASA Astrophysics Data System (ADS)

Bewicz, Anna; Musiał, Monika; Kucharski, Stanisław A.

2017-11-01

The equation-of-motion coupled-cluster method for electron affinity calculations has been used to study potential energy curves (PECs) for the Na+2 molecular ion. Although the studied molecule represents the open shell system the applied approach employs the closed shell Na+ 22 ion as the reference. In addition the Na+ 22 system dissociates into the closed shell fragments; hence, the restricted Hartree-Fock scheme can be used within the whole range of interatomic distances, from 2 to 45 Å. We used large basis set engaging 268 basis functions with all 21 electrons correlated. The relativistic effects are included via second-order Douglas-Kroll method. The computed PECs, spectroscopic molecular constants and vibrational energy levels agree well with experimental values if the latter are available or with other theoretical data.

X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates

DOE PAGES

Yin, Panchao; Wu, Bin; Mamontov, Eugene; ...

2016-02-05

A typical type of core-shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small angle X-ray scattering is used to study the structural features and stability of the core-shell structures in aqueous solutions. Time-resolved small angle X-ray scattering is applied to monitor the synthetic reactions and a three-stage formation mechanism is proposed to describe the synthesis of the core-shell polyoxometalates based on the monitoring results. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core-shell structures and two different types ofmore » water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures. A typical type of core shell polyoxometalates can be obtained through the Keggin-type polyoxometalate-templated growth of a layer of spherical shell structure of {Mo 72Fe 30}. Small-angle X-ray scattering is used to study the structural features and stability of the core shell structures in aqueous solutions. Time-resolved small-angle X-ray scattering is applied to monitor the synthetic reactions, and a three-stage formation mechanism is proposed to describe the synthesis of the core shell polyoxometalates based on the monitoring results. New protocols have been developed by fitting the X-ray data with custom physical models, which provide more convincing, objective, and completed data interpretation. Quasi-elastic and inelastic neutron scattering are used to probe the dynamics of water molecules in the core shell structures, and two different types of water molecules, the confined and structured water, are observed. These water molecules play an important role in bridging core and shell structures and stabilizing the cluster structures.« less

Equatorial and Apical Solvent Shells of the UO₂²⁺ Ion.

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

Nichols, Pat; Bylaska, Eric J.; Schenter, Gregory K.

2008-03-08

First principles molecular dynamics simulations of the hydration shells surrounding UO₂²⁺ ions are reported for temperatures near 300 K. Most of the simulations were done with 64 solvating water molecules (22 ps). Simulations with 122 water molecules (9 ps) were also carried out. The hydration structure predicted from the simulations was found to agree very well known results from X-ray data. The average U=O bond length was found to be 1.77Å . The first hydration shell contained five trigonally coordinated water molecules that were equatorially oriented about the O-U-O axis with the hydrogen atoms oriented away from the uranium atom.more » The five waters in the first shell were located at an average distance of 2.44Å (2.46Å - 122 water simulation). The second hydration shell was composed of distinct equatorial and apical regions resulting in a peak in the U-O radial distribution function at 4.59Å. The equatorial second shell contained 10 water molecules hydrogen-bonded to the five first shell molecules. Above and below the UO₂²⁺ ion, the water molecules were found to be significantly less structured. In these apical regions, water molecules were found to sporadically hydrogen bond to the oxygen atoms of the UO₂²⁺; oriented in such way as to have their protons pointed towards the cation. While the number of apical waters varied greatly, an average of 5-6 waters was found in this region. Many water transfers into and out of the equatorial and apical second solvation shells were observed to occur on a picosecond (ps) time scale via dissociative mechanisms. Beyond these shells, the bonding pattern substantially returned to the tetrahedral structure of bulk water.« less

A molecular dynamics study of the relaxation of an excited molecule in crystalline nitromethane

NASA Astrophysics Data System (ADS)

Rivera-Rivera, Luis A.; Siavosh-Haghighi, Ali; Sewell, Thomas D.; Thompson, Donald L.

2014-07-01

Classical molecular dynamics simulations were used to study the relaxation of an excited nitromethane molecule in perfect crystalline nitromethane at 250 K and 1 atm pressure. The molecule was instantaneously excited by statistically distributing energy E∗ between 25.0 kcal/mol and 125.0 kcal/mol among the 21 degrees of freedom of the molecule. The relaxation occurs exponentially with time constants between 11.58 ps and 13.57 ps. Energy transfer from the excited molecule to surrounding quasi-spherical shells of molecules occurs concurrently to both the nearest and next-nearest neighbor shells, but with more energy per molecule transferred more rapidly to the first shell.

Spontaneous formation of GaN/AlN core-shell nanowires on sapphire by hydride vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Trassoudaine, Agnès; Roche, Elissa; Bougerol, Catherine; André, Yamina; Avit, Geoffrey; Monier, Guillaume; Ramdani, Mohammed Réda; Gil, Evelyne; Castelluci, Dominique; Dubrovskii, Vladimir G.

2016-11-01

Spontaneous GaN/AlN core-shell nanowires with high crystal quality were synthesized on sapphire substrates by vapor-liquid-solid hydride vapor phase epitaxy (VLS-HVPE) without any voluntary aluminum source. Deposition of aluminum is difficult to achieve in this growth technique which uses metal-chloride gaseous precursors: the strong interaction between the AlCl gaseous molecules and the quartz reactor yields a huge parasitic nucleation on the walls of the reactor upstream the substrate. We open up an innovative method to produce GaN/AlN structures by HVPE, thanks to aluminum etching from the sapphire substrate followed by redeposition onto the sidewalls of the GaN core. The paper presents the structural characterization of GaN/AlN core-shell nanowires, speculates on the growth mechanism and discusses a model which describes this unexpected behavior.

Structure and dynamics of the hydration shells of the Al3+ ion

NASA Astrophysics Data System (ADS)

Bylaska, Eric J.; Valiev, Marat; Rustad, James R.; Weare, John H.

2007-03-01

First principles simulations of the hydration shells surrounding Al3+ ions are reported for temperatures near 300°C. The predicted six water molecules in the octahedral first hydration shell were found to be trigonally coordinated via hydrogen bonds to 12s shell water molecules in agreement with the putative structure used to analyze the x-ray data, but in disagreement with the results reported from conventional molecular dynamics using two-and three-body potentials. Bond lengths and angles of the water molecules in the first and second hydration shells and the average radii of these shells also agreed very well with the results of the x-ray analysis. Water transfers into and out of the second solvation shell were observed to occur on a picosecond time scale via a dissociative mechanism. Beyond the second shell the bonding pattern substantially returned to the tetrahedral structure of bulk water. Most of the simulations were done with 64 solvating water molecules (20ps). Limited simulations with 128 water molecules (7ps) were also carried out. Results agreed as to the general structure of the solvation region and were essentially the same for the first and second shell. However, there were differences in hydrogen bonding and Al-O radial distribution function in the region just beyond the second shell. At the end of the second shell a nearly zero minimum in the Al-O radial distribution was found for the 128 water system. This minimum is less pronounced minimum found for the 64 water system, which may indicate that sizes larger than 64 may be required to reliably predict behavior in this region.

Discrimination Between Closed and Open Shell (Turkish) Pistachio Nuts Using Undecimated Wavelet Packet Transform

USDA-ARS?s Scientific Manuscript database

Due to low consumer acceptance and the possibility of immature kernels, closed-shell pistachio nuts should be separated from open-shell nuts before reaching the consumer. The feasibility of a system using impact acoustics as a means of classifying closed-shell nuts from open-shell nuts has already b...

Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings.

PubMed

Burrezo, Paula Mayorga; Lin, Nai-Ti; Nakabayashi, Koji; Ohkoshi, Shin-Ichi; Calzado, Eva M; Boj, Pedro G; Díaz García, María A; Franco, Carlos; Rovira, Concepciò; Veciana, Jaume; Moos, Michael; Lambert, Christoph; López Navarrete, Juan T; Tsuji, Hayato; Nakamura, Eiichi; Casado, Juan

2017-03-06

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet-triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystalline p-hydroxyacetanilide (paracetamol) and gold core-shell structure as a model drug deliverable organic-inorganic hybrid nanostructure

NASA Astrophysics Data System (ADS)

Das, Subhojit; Paul, Anumita; Chattopadhyay, Arun

2013-09-01

We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release.We report on the generation of core-shell nanoparticles (NPs) having an organic nanocrystal (NC) core coated with an inorganic metallic shell, being dispersed in aqueous medium. First, NCs of p-hydroxyacetanilide (pHA)--known also as paracetamol--were generated in an aqueous medium. Transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) evidenced the formation of pHA NCs and of their crystalline nature. The NCs were then coated with Au to form pHA@Au core-shell NPs, where the thickness of the Au shell was on the order of nanometers. The formation of Au nanoshell--surrounding pHA NC--was confirmed from its surface plasmon resonance (SPR) band in the UV/Vis spectrum and by TEM measurements. Further, on treatment of the core-shell particles with a solution comprising NaCl and HCl (pH < 3), the Au shell could be dissolved, subsequently releasing pHA molecules. The dissolution of Au shell was marked by a gradual diminishing of its SPR band, while the release of pHA molecules in the solution was confirmed from TEM and FTIR studies. The findings suggest that the core-shell NP could be hypothesized to be a model for encapsulating drug molecules, in their crystalline forms, for slow as well as targeted release. Electronic supplementary information (ESI) available: See DOI: 10.1039/c3nr03566b

First-order symmetry-adapted perturbation theory for multiplet splittings.

PubMed

Patkowski, Konrad; Żuchowski, Piotr S; Smith, Daniel G A

2018-04-28

We present a symmetry-adapted perturbation theory (SAPT) for the interaction of two high-spin open-shell molecules (described by their restricted open-shell Hartree-Fock determinants) resulting in low-spin states of the complex. The previously available SAPT formalisms, except for some system-specific studies for few-electron complexes, were restricted to the high-spin state of the interacting system. Thus, the new approach provides, for the first time, a SAPT-based estimate of the splittings between different spin states of the complex. We have derived and implemented the lowest-order SAPT term responsible for these splittings, that is, the first-order exchange energy. We show that within the so-called S 2 approximation commonly used in SAPT (neglecting effects that vanish as fourth or higher powers of intermolecular overlap integrals), the first-order exchange energies for all multiplets are linear combinations of two matrix elements: a diagonal exchange term that determines the spin-averaged effect and a spin-flip term responsible for the splittings between the states. The numerical factors in this linear combination are determined solely by the Clebsch-Gordan coefficients: accordingly, the S 2 approximation implies a Heisenberg Hamiltonian picture with a single coupling strength parameter determining all the splittings. The new approach is cast into both molecular-orbital and atomic-orbital expressions: the latter enable an efficient density-fitted implementation. We test the newly developed formalism on several open-shell complexes ranging from diatomic systems (Li⋯H, Mn⋯Mn, …) to the phenalenyl dimer.

First-order symmetry-adapted perturbation theory for multiplet splittings

NASA Astrophysics Data System (ADS)

Patkowski, Konrad; Żuchowski, Piotr S.; Smith, Daniel G. A.

2018-04-01

We present a symmetry-adapted perturbation theory (SAPT) for the interaction of two high-spin open-shell molecules (described by their restricted open-shell Hartree-Fock determinants) resulting in low-spin states of the complex. The previously available SAPT formalisms, except for some system-specific studies for few-electron complexes, were restricted to the high-spin state of the interacting system. Thus, the new approach provides, for the first time, a SAPT-based estimate of the splittings between different spin states of the complex. We have derived and implemented the lowest-order SAPT term responsible for these splittings, that is, the first-order exchange energy. We show that within the so-called S2 approximation commonly used in SAPT (neglecting effects that vanish as fourth or higher powers of intermolecular overlap integrals), the first-order exchange energies for all multiplets are linear combinations of two matrix elements: a diagonal exchange term that determines the spin-averaged effect and a spin-flip term responsible for the splittings between the states. The numerical factors in this linear combination are determined solely by the Clebsch-Gordan coefficients: accordingly, the S2 approximation implies a Heisenberg Hamiltonian picture with a single coupling strength parameter determining all the splittings. The new approach is cast into both molecular-orbital and atomic-orbital expressions: the latter enable an efficient density-fitted implementation. We test the newly developed formalism on several open-shell complexes ranging from diatomic systems (Li⋯H, Mn⋯Mn, …) to the phenalenyl dimer.

Open-shell characters and second hyperpolarizabilities of one-dimensional graphene nanoflakes composed of trigonal graphene units.

PubMed

Yoneda, Kyohei; Nakano, Masayoshi; Fukui, Hitoshi; Minami, Takuya; Shigeta, Yasuteru; Kubo, Takashi; Botek, Edith; Champagne, Benoît

2011-06-20

The impact of topology on the open-shell characters and the second hyperpolarizabilities (γ) has been addressed for one-dimensional graphene nanoflakes (GNFs) composed of the smallest trigonal graphene (phenalenyl) units. The main results are: 1) These GNFs show not only diradical but also multiradical characters when increasing the number of linked units. 2) GNFs composed of an equivalent number of units can exhibit a wide range of open-shell characters-from nearly closed-shell to pure multiradical characters-depending on the linking pattern of the trigonal units. 3) This wide variation in open-shell characters is explained by their resonance structures and/or by their (HOMO-i)-(LUMO+i) gaps deduced from the orbital correlations. 4) The change in the linking structure of the units can effectively control their open-shell characters as well as their γ values, of which the longitudinal components are significantly enhanced for the singlet GNFs having intermediate open-shell characters. 5) Singlet alternately linked (AL) systems present intermediate multiradical characters even in the case of a large number of units, which creates a significant enhancement of γ with increasing the size, whereas nonalternately linked (NAL) systems, which present pure multiradical characters, possess much smaller γ values. Finally 6) by switching from the singlet to the highest spin states, the γ values of NAL systems hardly change, whereas those of AL systems exhibit large reductions. These fascinating structure-property relationships between the topology of the GNFs, their open-shell characters, and their γ values not only deepen the understanding of open-shell characters of GNFs but aim also at stimulating further design studies to achieve giant NLO responses based on open-shell graphene-like materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Core-shell designed scaffolds for drug delivery and tissue engineering.

PubMed

Perez, Roman A; Kim, Hae-Won

2015-07-01

Scaffolds that secure and deliver therapeutic ingredients like signaling molecules and stem cells hold great promise for drug delivery and tissue engineering. Employing a core-shell design for scaffolds provides a promising solution. Some unique methods, such as co-concentric nozzle extrusion, microfluidics generation, and chemical confinement reactions, have been successful in producing core-shelled nano/microfibers and nano/microspheres. Signaling molecules and drugs, spatially allocated to the core and/or shell part, can be delivered in a controllable and sequential manner for optimal therapeutic effects. Stem cells can be loaded within the core part on-demand, safely protected from the environments, which ultimately affords ex vivo culture and in vivo tissue engineering. The encapsulated cells experience three-dimensional tissue-mimic microenvironments in which therapeutic molecules are secreted to the surrounding tissues through the semi-permeable shell. Tuning the material properties of the core and shell, changing the geometrical parameters, and shaping them into proper forms significantly influence the release behaviors of biomolecules and the fate of the cells. This topical issue highlights the immense usefulness of core-shell designs for the therapeutic actions of scaffolds in the delivery of signaling molecules and stem cells for tissue regeneration and disease treatment. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polarization and charge transfer in the hydration of chloride ions

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

Zhao Zhen; Rogers, David M.; Beck, Thomas L.

2010-01-07

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters.more » The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.« less

Ab initio investigation of the first hydration shell of protonated glycine

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

Wei, Zhichao; Chen, Dong, E-mail: dongchen@henu.edu.cn, E-mail: boliu@henu.edu.cn; Zhao, Huiling

2014-02-28

The first hydration shell of the protonated glycine is built up using Monte Carlo multiple minimum conformational search analysis with the MMFFs force field. The potential energy surfaces of the protonated glycine and its hydration complexes with up to eight water molecules have been scanned and the energy-minimized structures are predicted using the ab initio calculations. First, three favorable structures of protonated glycine were determined, and the micro-hydration processes showed that water can significantly stabilize the unstable conformers, and then their first hydration shells were established. Finally, we found that seven water molecules are required to fully hydrate the firstmore » hydration shell for the most stable conformer of protonated glycine. In order to analyse the hydration process, the dominant hydration sites located around the ammonium and carboxyl groups are studied carefully and systemically. The results indicate that, water molecules hydrate the protonated glycine in an alternative dynamic hydration process which is driven by the competition between different hydration sites. The first three water molecules are strongly attached by the ammonium group, while only the fourth water molecule is attached by the carboxyl group in the ultimate first hydration shell of the protonated glycine. In addition, the first hydration shell model has predicted most identical structures and a reasonable accord in hydration energy and vibrational frequencies of the most stable conformer with the conductor-like polarizable continuum model.« less

HF in clusters of molecular hydrogen. I. Size evolution of quantum solvation by parahydrogen molecules.

PubMed

Jiang, Hao; Bacić, Zlatko

2005-06-22

We present a theoretical study of the quantum solvation of the HF molecule by a small number of parahydrogen molecules, having n = 1-13 solvent particles. The minimum-energy cluster structures determined for n = 1-12 have all of the H(2) molecules in the first solvent shell. The first solvent shell closes at n = 12 and its geometry is icosahedral, with the HF molecule at the center. The quantum-mechanical ground-state properties of the clusters are calculated exactly using the diffusion Monte Carlo method. The zero-point energy of (p-H(2))(n)HF clusters is unusually large, amounting to 86% of the potential well depth for n > 7. The radial probability distribution functions (PDFs) confirm that the first solvent shell is complete for n = 12, and that the 13th p-H(2) molecule begins to fill the second solvent shell. The p-H(2) molecules execute large-amplitude motions and are highly mobile, making the solvent cage exceptionally fluxional. The anisotropy of the solvent, very pronounced for small clusters, decreases rapidly with increasing n, so that for n approximately 8-9 the solvent environment is practically isotropic. The analysis of the pair angular PDF reveals that for a given n, the parahydrogen solvent density around the HF is modulated in a pattern which clearly reflects the lowest-energy cluster configuration. The rigidity of the solvent clusters displays an interesting size dependence, increasing from n = 6 to 9, becoming floppier for n = 10, and increasing again up to n = 12, as the solvent shell is filled. The rigidity of the solvent cage appears to reach its maximum for n = 12, the point at which the first solvent shell is closed.

Simulations of polymorphic icosahedral shells assembling around many cargo molecules

NASA Astrophysics Data System (ADS)

Mohajerani, Farzaneh; Perlmutter, Jason; Hagan, Michael

Bacterial microcompartments (BMCs) are large icosahedral shells that sequester the enzymes and reactants responsible for particular metabolic pathways in bacteria. Although different BMCs vary in size and encapsulate different cargoes, they are constructed from similar pentameric and hexameric shell proteins. Despite recent groundbreaking experiments which visualized the formation of individual BMCs, the detailed assembly pathways and the factors which control shell size remain unclear. In this talk, we describe theoretical and computational models that describe the dynamical encapsulation of hundreds of cargo molecules by self-assembling icosahedral shells. We present phase diagrams and analysis of dynamical simulation trajectories showing how the thermodynamics, assembly pathways, and emergent structures depend on the interactions among shell proteins and cargo molecules. Our model suggests a mechanism for controlling insertion of the 12 pentamers required for a closed shell topology, and the relationship between assembly pathway and BMC size polydispersity. In addition to elucidating how native BMCs assemble,our results establish principles for reengineering BMCs or viral capsids as customizable nanoreactors that can assemble around a programmable set of enzymes and reactants. Supported by NIH R01GM108021 and Brandeis MRSEC DMR-1420382.

Development of hydrogel TentaGel shell-core beads for ultrahigh throughput solution-phase screening of encoded OBOC combinatorial small molecule libraries.

PubMed

Baek, Hyoung Gee; Liu, Ruiwu; Lam, Kit S

2009-01-01

The one-bead one-compound (OBOC) combinatorial library method enables the rapid generation and screening of millions of discrete chemical compounds on beads. Most of the OBOC screening methods require the library compounds to remain tethered to the bead during screening process. Methods have also been developed to release library compounds from immobilized beads for in situ solution phase or "lawn" assays. However, this latter approach, while extremely powerful, is severely limited by the lack of suitable solid supports for such assays. Here, we report on the development of a novel hydrogel TentaGel shell-core (HTSC) bead in which hydrogel is grafted onto the polystyrene-based TentaGel (TG) bead as an outer shell (5-80 mum thick) via free radical surface-initiated polymerization. This novel shell-core bilayer resin enables the preparation of encoded OBOC combinatorial small molecule libraries, such that the library compounds reside on the highly hydrophilic outer layer and the coding tags reside in the polystyrene-based TG core. Using fluorescein as a model small molecule compound, we have demonstrated that fluorescein molecules that have been linked covalently to the hydrogel shell via a disulfide bond could readily diffuse out of the hydrogel layer into the bead surrounding after reduction with dithiothreitol. In contrast, under identical condition, the released fluorescein molecules remained bound to unmodified TG bead. We have prepared an encoded OBOC small molecule library on the novel shell-core beads and demonstrated that the beads can be readily decoded.

Amphiphilic Block Copolymers Directed Interface Coassembly to Construct Multifunctional Microspheres with Magnetic Core and Monolayer Mesoporous Aluminosilicate Shell.

PubMed

Zhang, Yu; Yue, Qin; Yu, Lei; Yang, Xuanyu; Hou, Xiu-Feng; Zhao, Dongyuan; Cheng, Xiaowei; Deng, Yonghui

2018-05-11

Core-shell magnetic porous microspheres have wide applications in drug delivery, catalysis and bioseparation, and so on. However, it is great challenge to controllably synthesize magnetic porous microspheres with uniform well-aligned accessible large mesopores (>10 nm) which are highly desired for applications involving immobilization or adsorption of large guest molecules or nanoobjects. In this study, a facile and general amphiphilic block copolymer directed interfacial coassembly strategy is developed to synthesize core-shell magnetic mesoporous microspheres with a monolayer of mesoporous shell of different composition, such as core-shell magnetic mesoporous aluminosilicate (CS-MMAS), silica (CS-MMS), and zirconia-silica (CS-MMZS), open and large pores by employing polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP) as an interface structure directing agent and aluminum acetylacetonate (Al(acac) 3 ), zirconium acetylacetonate, and tetraethyl orthosilicate as shell precursors. The obtained CS-MMAS microspheres possess magnetic core, perpendicular mesopores (20-32 nm) in the shell, high surface area (244.7 m 2 g -1 ), and abundant acid sites (0.44 mmol g -1 ), and as a result, they exhibit superior performance in removal of organophosphorus pesticides (fenthion) with a fast adsorption dynamics and high adsorption capacity. CS-MMAS microspheres loaded with Au nanoparticles (≈3.5 nm) behavior as a highly active heterogeneous nanocatalyst for N-alkylation reaction for producing N-phenylbenzylamine with a selectivity and yields of over 90% and good magnetic recyclability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Excimers from stable and persistent supramolecular radical-pairs in red/NIR-emitting organic nanoparticles and polymeric films.

PubMed

Blasi, Davide; Nikolaidou, Domna M; Terenziani, Francesca; Ratera, Imma; Veciana, Jaume

2017-03-29

In this work, the luminescence properties of new materials based on open-shell molecular systems are studied. In particular, we prepared polymeric films and organic nanoparticles (ONPs) doped with triphenylmethyl radical molecules. ONPs exhibit a uniform size distribution, spherical morphology and high colloidal stability. The emission spectrum of low-doped ONP suspensions and low-doped films is very similar to the emission spectrum of TTM in solution, while the luminescence lifetime and the luminescence quantum yield (LQY) are highly increased. Increasing the radical doping leads to a progressive decrease of the LQY and the appearance of a new broad excimeric band at longer wavelengths, both for ONPs and films. Thus, not only the luminescence properties were improved, but also the formation of excimers from stable and persistent supramolecular radical-pairs was observed for the first time. The good stability and luminescence properties with emission in the red-NIR region (650-800 nm), together with the open-shell nature of the emitter, make these free-radical excimer-forming materials promising candidates for optoelectronic and bioimaging applications.

Hydration shell parameters of aqueous alcohols: THz excess absorption and packing density.

PubMed

Matvejev, V; Zizi, M; Stiens, J

2012-12-06

Solvation in water requires minimizing the perturbations in its hydrogen bonded network. Hence solutes distort water molecular motions in a surrounding domain, forming a molecule-specific hydration shell. The properties of those hydration shells impact the structure and function of the solubilized molecules, both at the single molecule and at higher order levels. The size of the hydration shell and the picoseconds time-scale water dynamics retardation are revealed by terahertz (THz) absorption coefficient measurements. Room-temperature absorption coefficient at f = 0.28 [THz] is measured as a function of alcohol concentration in aqueous methanol, ethanol, 1,2-propanol, and 1-butanol solutions. Highly diluted alcohol measurements and enhanced overall measurement accuracy are achieved with a THz absorption measurement technique of nL-volume liquids in a capillary tube. In the absorption analysis, bulk and interfacial molecular domains of water and alcohol are considered. THz ideal and excess absorption coefficients are defined in accordance with thermodynamics mixing formulations. The parameter extraction method is developed based on a THz excess absorption model and hydrated solute molecule packing density representation. First, the hydration shell size is deduced from the hydrated solute packing densities at two specific THz excess absorption nonlinearity points: at infinite alcohol dilution (IAD) and at the THz excess absorption extremum (EAE). Consequently, interfacial water and alcohol molecular domain absorptions are deduced from the THz excess absorption model. The hydration shell sizes obtained at the THz excess absorption extremum are in excellent agreement with other reports. The hydration shells of methanol, ethanol, 1- and 2-propanol consist of 13.97, 22.94, 22.99, and 31.10 water molecules, respectively. The hydration shell water absorption is on average 0.774 ± 0.028 times the bulk water absorption. The hydration shell parameters might shed light on hydration dynamics of biomolecules.

Dock 'n roll: folding of a silk-inspired polypeptide into an amyloid-like beta solenoid.

PubMed

Zhao, Binwu; Cohen Stuart, Martien A; Hall, Carol K

2016-04-20

Polypeptides containing the motif ((GA)mGX)n occur in silk and have a strong tendency to self-assemble. For example, polypeptides containing (GAGAGAGX)n, where X = G or H have been observed to form filaments; similar sequences but with X = Q have been used in the design of coat proteins (capsids) for artificial viruses. The structure of the (GAGAGAGX)m filaments has been proposed to be a stack of peptides in a β roll structure with the hydrophobic side chains pointing outwards (hydrophobic shell). Another possible configuration, a β roll or β solenoid structure which has its hydrophobic side chains buried inside (hydrophobic core) was, however, overlooked. We perform ground state analysis as well as atomic-level molecular dynamics simulations, both on single molecules and on two-molecule stacks of the silk-inspired sequence (GAGAGAGQ)10, to decide whether the hydrophobic core or the hydrophobic shell configuration is the most stable one. We find that a stack of two hydrophobic core molecules is energetically more favorable than a stack of two hydrophobic shell molecules. A shell molecule initially placed in a perfect β roll structure tends to rotate its strands, breaking in-plane hydrogen bonds and forming out-of-plane hydrogen bonds, while a core molecule stays in the β roll structure. The hydrophobic shell structure has type II' β turns whereas the core configuration has type II β turns; only the latter secondary structure agrees well with solid-state NMR experiments on a similar sequence (GA)15. We also observe that the core stack has a higher number of intra-molecular hydrogen bonds and a higher number of hydrogen bonds between stack and water than the shell stack. Hence, we conclude that the hydrophobic core configuration is the most likely structure. In the stacked state, each peptide has more intra-molecular hydrogen bonds than a single folded molecule, which suggests that stacking provides the extra stability needed for molecules to reach the folded state.

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

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Effect of vertebral shell on injection pressure and intravertebral pressure in vertebroplasty.

PubMed

Baroud, Gamal; Vant, Christianne; Giannitsios, Demetri; Bohner, Marc; Steffen, Thomas

2005-01-01

An experimental biomechanical study conducted on osteoporotic cadaveric vertebrae. 1) To measure the intravertebral shell pressure and injection pressure; and 2) to determine the effect of the vertebral shell on the intravertebral shell pressure and on the injection pressure. Forces that govern cement flow are an essential component of the cement injection process in vertebroplasty. The vertebral shell may play a significant role in confining the flow of cement in the vertebral body and thereby affecting the intravertebral pressure and injection pressure. A small fenestration was created in the left lateral vertebral shell of 14 vertebrae. A valve to open and close the fenestration and a sensor to measure the intravertebral pressure were attached to the opening. A closed fenestration simulated an intact shell, whereas an open fenestration represented a vented shell. Injection pressure and intravertebral pressure at the shell were recorded during a controlled injection. A closed fenestration resulted in a significant increase in the intravertebral pressure at the shell. During the injection, the shell pressure increased on average to approximately 3.54 +/- 2.91 kPa. Conversely, an open fenestration resulted in an instant relaxation of the shell pressure to the ambient pressure of 0 kPa. Additionally, the injection pressure was approximately 97 times higher than the shell pressure. The presence of vertebral shell seems to be important for intravertebral pressure. However, the intravertebral shell pressure adds very little to the injection pressure.

The equation-of-motion coupled cluster method for triple electron attached states

NASA Astrophysics Data System (ADS)

Musiał, Monika; Olszówka, Marta; Lyakh, Dmitry I.; Bartlett, Rodney J.

2012-11-01

The initial implementation of the triple electron attachment (TEA) equation-of-motion (EOM) coupled cluster (CC) method is presented, aiming at the description of electronic states with three open shell electrons outside a suitably chosen closed shell vacuum. In particular, such an approach can be used for describing dissociation of chemical bonds predominantly formed by three valence electrons, for example, in LiC and NaC molecules. Both ground and excited states are considered while rigorously maintaining the correct spin value. The preliminary results show a correct asymptotic behavior of the dissociation curves. At the same time, we emphasize that a chemically accurate description will require an extension of the minimal TEA-EOM-CC model introduced here, analogous to those already used in the double ionization potential and double electron attachment methods.

An explicitly spin-free compact open-shell coupled cluster theory using a multireference combinatoric exponential ansatz: formal development and pilot applications.

PubMed

Datta, Dipayan; Mukherjee, Debashis

2009-07-28

In this paper, we present a comprehensive account of an explicitly spin-free compact state-universal multireference coupled cluster (CC) formalism for computing the state energies of simple open-shell systems, e.g., doublets and biradicals, where the target open-shell states can be described by a few configuration state functions spanning a model space. The cluster operators in this formalism are defined in terms of the spin-free unitary generators with respect to the common closed-shell component of all model functions (core) as vacuum. The spin-free cluster operators are either closed-shell-like n hole-n particle excitations (denoted by T(mu)) or involve excitations from the doubly occupied (nonvalence) orbitals to the singly occupied (valence) orbitals (denoted by S(e)(mu)). In addition, there are cluster operators with exchange spectator scatterings involving the valence orbitals (denoted by S(re)(mu)). We propose a new multireference cluster expansion ansatz for the wave operator with the above generally noncommuting cluster operators which essentially has the same physical content as the Jeziorski-Monkhorst ansatz with the commuting cluster operators defined in the spin-orbital basis. The T(mu) operators in our ansatz are taken to commute with all other operators, while the S(e)(mu) and S(re)(mu) operators are allowed to contract among themselves through the spectator valence orbitals. An important innovation of this ansatz is the choice of an appropriate automorphic factor accompanying each contracted composite of cluster operators in order to ensure that each distinct excitation generated by this composite appears only once in the wave operator. The resulting CC equations consist of two types of terms: a "direct" term and a "normalization" term containing the effective Hamiltonian operator. It is emphasized that the direct term is almost quartic in the cluster amplitudes, barring only a handful of terms and termination of the normalization term depends on the valence rank of the effective Hamiltonian operator and the excitation rank of the cluster operators at which the theory is truncated. Illustrative applications are presented by computing the state energies of neutral doublet radicals and doublet molecular cations and ionization energies of neutral molecules and comparing our results with the other open-shell CC theories, benchmark full CI results (when available) in the same basis, and the experimental results. Highly encouraging results show the efficacy of the method.

Orbital-optimized MP2.5 and its analytic gradients: Approaching CCSD(T) quality for noncovalent interactions

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

Bozkaya, Uğur, E-mail: ugur.bozkaya@atauni.edu.tr; Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, and School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332; Sherrill, C. David

2014-11-28

Orbital-optimized MP2.5 [or simply “optimized MP2.5,” OMP2.5, for short] and its analytic energy gradients are presented. The cost of the presented method is as much as that of coupled-cluster singles and doubles (CCSD) [O(N{sup 6}) scaling] for energy computations. However, for analytic gradient computations the OMP2.5 method is only half as expensive as CCSD because there is no need to solve λ{sub 2}-amplitude equations for OMP2.5. The performance of the OMP2.5 method is compared with that of the standard second-order Møller–Plesset perturbation theory (MP2), MP2.5, CCSD, and coupled-cluster singles and doubles with perturbative triples (CCSD(T)) methods for equilibrium geometries, hydrogenmore » transfer reactions between radicals, and noncovalent interactions. For bond lengths of both closed and open-shell molecules, the OMP2.5 method improves upon MP2.5 and CCSD by 38%–43% and 31%–28%, respectively, with Dunning's cc-pCVQZ basis set. For complete basis set (CBS) predictions of hydrogen transfer reaction energies, the OMP2.5 method exhibits a substantially better performance than MP2.5, providing a mean absolute error of 1.1 kcal mol{sup −1}, which is more than 10 times lower than that of MP2.5 (11.8 kcal mol{sup −1}), and comparing to MP2 (14.6 kcal mol{sup −1}) there is a more than 12-fold reduction in errors. For noncovalent interaction energies (at CBS limits), the OMP2.5 method maintains the very good performance of MP2.5 for closed-shell systems, and for open-shell systems it significantly outperforms MP2.5 and CCSD, and approaches CCSD(T) quality. The MP2.5 errors decrease by a factor of 5 when the optimized orbitals are used for open-shell noncovalent interactions, and comparing to CCSD there is a more than 3-fold reduction in errors. Overall, the present application results indicate that the OMP2.5 method is very promising for open-shell noncovalent interactions and other chemical systems with difficult electronic structures.« less

Staged depressurization system

DOEpatents

Schulz, T.L.

1993-11-02

A nuclear reactor having a reactor vessel disposed in a containment shell is depressurized in stages using depressurizer valves coupled in fluid communication with the coolant circuit. At least one sparger submerged in the in-containment refueling water storage tank which can be drained into the containment sump communicates between one or more of the valves and an inside of the containment shell. The depressurizer valves are opened in stages, preferably at progressively lower coolant levels and for opening progressively larger flowpaths to effect depressurization through a number of the valves in parallel. The valves can be associated with a pressurizer tank in the containment shell, coupled to a coolant outlet of the reactor. At least one depressurization valve stage openable at a lowest pressure is coupled directly between the coolant circuit and the containment shell. The reactor is disposed in the open sump in the containment shell, and a further valve couples the open sump to a conduit coupling the refueling water storage tank to the coolant circuit for adding water to the coolant circuit, whereby water in the containment shell can be added to the reactor from the open sump. 4 figures.

Staged depressurization system

DOEpatents

Schulz, Terry L.

1993-01-01

A nuclear reactor having a reactor vessel disposed in a containment shell is depressurized in stages using depressurizer valves coupled in fluid communication with the coolant circuit. At least one sparger submerged in the in-containment refueling water storage tank which can be drained into the containment sump communicates between one or more of the valves and an inside of the containment shell. The depressurizer valves are opened in stages, preferably at progressively lower coolant levels and for opening progressively larger flowpaths to effect depressurization through a number of the valves in parallel. The valves can be associated with a pressurizer tank in the containment shell, coupled to a coolant outlet of the reactor. At least one depressurization valve stage openable at a lowest pressure is coupled directly between the coolant circuit and the containment shell. The reactor is disposed in the open sump in the containment shell, and a further valve couples the open sump to a conduit coupling the refueling water storage tank to the coolant circuit for adding water to the coolant circuit, whereby water in the containment shell can be added to the reactor from the open sump.

An extension of the fenske-hall LCAO method for approximate calculations of inner-shell binding energies of molecules

NASA Astrophysics Data System (ADS)

Zwanziger, Ch.; Reinhold, J.

1980-02-01

The approximate LCAO MO method of Fenske and Hall has been extended to an all-election method allowing the calculation of inner-shell binding energies of molecules and their chemical shifts. Preliminary results are given.

Characterization of the organic ligand shell of semiconductor quantum dots by fluorescence quenching experiments.

PubMed

Boldt, Klaus; Jander, Sebastian; Hoppe, Kathrin; Weller, Horst

2011-10-25

We present the characterization of the organic ligand shell of CdSe/Cd(x)Zn(1-x)S/ZnS nanoparticles by means of fluorescence quenching experiments. Both electron scavengers and acceptors for resonance energy transfer were employed as probes. Different quenching behavior for short and long chain thiol ligands in water was found. It could be shown that poly(ethylene oxide) (PEO)-capping of the particles comprises a densely packed inner shell and a loosely packed outer shell in which ions and small molecules diffuse unhindered. A quantitative uptake of quencher molecules into the PEO shell was observed, through which the particle volume including the ligand sphere could be determined.

Effects of the microbubble shell physicochemical properties on ultrasound-mediated drug delivery to the brain.

PubMed

Wu, Shih-Ying; Chen, Cherry C; Tung, Yao-Sheng; Olumolade, Oluyemi O; Konofagou, Elisa E

2015-08-28

Lipid-shelled microbubbles have been used in ultrasound-mediated drug delivery. The physicochemical properties of the microbubble shell could affect the delivery efficiency since they determine the microbubble mechanical properties, circulation persistence, and dissolution behavior during cavitation. Therefore, the aim of this study was to investigate the shell effects on drug delivery efficiency in the brain via blood-brain barrier (BBB) opening in vivo using monodisperse microbubbles with different phospholipid shell components. The physicochemical properties of the monolayer were varied by using phospholipids with different hydrophobic chain lengths (C16, C18, and C24). The dependence on the molecular size and acoustic energy (both pressure and pulse length) were investigated. Our results showed that a relatively small increase in the microbubble shell rigidity resulted in a significant increase in the delivery of 40-kDa dextran, especially at higher pressures. Smaller (3kDa) dextran did not show significant difference in the delivery amount, suggesting that the observed shell effect was molecular size-dependent. In studying the impact of acoustic energy on the shell effects, it was found that they occurred most significantly at pressures causing microbubble destruction (450kPa and 600kPa); by increasing the pulse length to deliver the 40-kDa dextran, the difference between C16 and C18 disappeared while C24 still achieved the highest delivery efficiency. These indicated that the acoustic energy could be used to modulate the shell effects. The acoustic cavitation emission revealed the physical mechanisms associated with different shells. Overall, lipid-shelled microbubbles with long hydrophobic chain length could achieve high delivery efficiency for larger molecules especially with high acoustic energy. Our study, for the first time, offered evidence directly linking the microbubble monolayer shell with their efficacy for drug delivery in vivo. Copyright © 2015 Elsevier B.V. All rights reserved.

Fullerene-like organization of HIV gag-protein shell in virus-like particles produced by recombinant baculovirus.

PubMed

Nermut, M V; Hockley, D J; Jowett, J B; Jones, I M; Garreau, M; Thomas, D

1994-01-01

Virus-like particles produced by a recombinant baculovirus containing the HIV gag gene were examined by negative staining after delipidization. This technique demonstrated that the gag-protein shell consisted of radially arranged short rods which formed a network of ring-like structures. Similar structures were observed at the plasma membrane of infected cells which had been opened by wet-cleaving. Occasionally five or six subunits were observed forming a ring. These findings suggest that the gag-encoded precursor (pr55) is a rod-like molecule about 34 A in diameter and 85 A in length. A protein cylinder of such dimensions would have a molecular weight of 56K. The center-to-center distance of two neighboring rings formed by the rods was 66 +/- 8 A (N = 200) by direct measurements and 65 A as obtained from averaged images. This morphology and these dimensions indicate that the virus-like particles contain the gag precursor in the form of a near-spherical "fullerene-like" icosahedral shell. Our data indicate that the triangulation number of the rings equals 63. However, since one rod of pr55 is shared by two rings, the number of copies of the precursor will be 1890 as opposed to 2522 if the molecules were closely packed. The particle diameter of 102 nm deduced from the proposed model was close to the diameter obtained from thin sections of low-temperature-embedded specimens (103-108 nm).

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

Ganesh, Panchapakesan; Kent, Paul R; Mochalin, Vadym N

We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less

Active ester functional single core magnetic nanostructures as a versatile immobilization matrix for effective bioseparation and catalysis.

PubMed

Gelbrich, Thorsten; Reinartz, Michael; Schmidt, Annette M

2010-03-08

Multifunctional nanocarriers for amino functional targets with a high density of accessible binding sites are obtained in a single polymerization step by grafting from copolymerization of an active ester monomer from superparamagnetic cores. As a result of the brush-like structure of the highly dispersed shell, the nano-objects exhibit an available capture capacity for amines that is found to be up to 2 orders of magnitude higher than for commercial magnetic beads, and the functional brush shell can serve as a template for many types of pendant functional groups and molecules. As comonomer, oligo(ethylene glycol) methacrylate allows for excellent water solubility at room temperature, biocompatibility, and thermoflocculation. We demonstrate the biorelated applicability of the hybrid nanoparticles by two different approaches. In the first approach, the immobilization of trypsin to the core-shell nanoparticles results in highly active, nanoparticulate biocatalysts that can easily be separated magnetically. Second, we demonstrate that the obtained nanoparticles are suitable for the effective labeling of cell membranes, opening a novel pathway for the easy and effective isolation of membrane proteins.

Dock ’n Roll: Folding of a Silk-Inspired Polypeptide into an Amyloid-like Beta Solenoid

PubMed Central

Zhao, Binwu; Cohen Stuart, Martien A.; Hall, Carol K.

2016-01-01

Polypeptides containing the motif ((GA)mGX)n occur in silk (we refer to them as ‘silk-like’) and have a strong tendency to self-assemble. For example, polypeptides containing (GAGAGAGX)n, where X = G or H have been observed to form filaments; similar sequences but with X = Q have been used in the design of coat proteins (capsids) for artificial viruses. The structure of the (GAGAGAGX)m filaments has been proposed to be a stack of peptides in a β roll structure with the hydrophobic side chains pointing outwards (hydrophobic shell). Another possible configuration, a β roll or β solenoid structure which has its hydrophobic side chains buried inside (hydrophobic core) was, however, overlooked. We perform ground state analysis as well as atomic-level molecular dynamics simulations, both on single molecules and on two-molecule stacks of the silk-inspired sequence (GAGAGAGQ)10, to decide whether the hydrophobic core or the hydrophobic shell configuration is the most stable one. We find that a stack of two hydrophobic core molecules is energetically more favorable than a stack of two shell molecules. A shell molecule initially placed in a perfect β roll structure tends to rotate its strands, breaking in-plane hydrogen bonds and forming out-of-plane hydrogen bonds, while a core molecule stays in the β roll structure. The hydrophobic shell structure has type II’ β turns whereas the core configuration has type II β turns; only the latter secondary structure agrees well with solid-state NMR experiments on a similar sequence (GA)15. We also observe that the core stack has a higher number of intra-molecular hydrogen bonds and a higher number of hydrogen bonds between stack and water than the shell stack. Hence, we conclude that the hydrophobic core configuration is the most likely structure. In the stacked state, each peptide has more intra-molecular hydrogen bonds than a single folded molecule, which suggests that stacking provides the extra stability needed for molecules to reach the folded state. PMID:26947809

Photoelectron Spectroscopy of Substituted Phenylnitrenes

NASA Astrophysics Data System (ADS)

Wijeratne, Neloni R.; Da Fonte, Maria; Wenthold, Paul G.

2009-06-01

Nitrenes are unusual molecular structures with unfilled electronic valences that are isoelectronic with carbenes. Although, both can be generated by either thermal or photochemical decomposition of appropriate precursors they usually exhibit different reactivities. In this work, we carry out spectroscopic studies of substituted phenylnitrene to determine how the introduction of substituents will affect the reactivity and its thermochemical properties. All studies were carried out by using the newly constructed time-of-flight negative ion photoelectron spectrometer (NIPES) at Purdue University. The 355 nm photoelectron spectra of the o-, m-, and p-chlorophenyl nitrene anions are fairly similar to that measured for phenylnitrene anion. All spectra show low energy triplet state and a high energy singlet state. The singlet state for the meta isomer is well-resolved, with a well defined origin and observable vibrational structure. Whereas the singlet states for the ortho and para isomers have lower energy onsets and no resolved structure. The isomeric dependence suggests that the geometry differences result from the resonance interaction between the nitrogen and the substituent. Quinoidal resonance structures are possible for the open-shell singlet states of the o- and p-chlorinated phenyl nitrenes. The advantages of this type of electronic structures for the open-shell singlet states is that the unpaired electrons can be more localized on separate atoms in the molecules, minimizing the repulsion between. Because the meta position is not in resonance with the nitrenes, substitution at that position should not affect the structure of the open-shell singlet state. The measured electron affinities (EA) of the triplet phenylnitrenes are in excellent agreement with the values predicted by electronic structure calculations. The largest EA, 1.82 eV is found for the meta isomer, with para being the smallest, 1.70 eV.

Cooperative effects in spherical spasers: Ab initio analytical model

NASA Astrophysics Data System (ADS)

Bordo, V. G.

2017-06-01

A fully analytical semiclassical theory of cooperative optical processes which occur in an ensemble of molecules embedded in a spherical core-shell nanoparticle is developed from first principles. Both the plasmonic Dicke effect and spaser generation are investigated for the designs in which a shell/core contains an arbitrarily large number of active molecules in the vicinity of a metallic core/shell. An essential aspect of the theory is an ab initio account of the feedback from the core/shell boundaries which significantly modifies the molecular dynamics. The theory provides rigorous, albeit simple and physically transparent, criteria for both plasmonic superradiance and surface plasmon generation.

Transition energy and potential energy curves for ionized inner-shell states of CO, O2 and N 2 calculated by several inner-shell multiconfigurational approaches.

PubMed

Moura, Carlos E V de; Oliveira, Ricardo R; Rocha, Alexandre B

2013-05-01

Potential energy curves and inner-shell ionization energies of carbon monoxide, oxygen and nitrogen molecules were calculated using several forms of the inner-shell multiconfigurational self-consistent field (IS-MCSCF) method-a recently proposed protocol to obtain specifically converged inner-shell states at this level. The particular forms of the IS-MCSCF method designated IS-GVB-PP, IS-FVBL and IS-CASSCF stand for perfect pairing generalized valence bond, full valence bond-like MCSCF and complete active space self consistent field, respectively. A comparison of these different versions of the IS-MCSCF method was carried out for the first time. The results indicate that inner-shell states are described accurately even for the simplest version of the method (IS-GVB-PP). Dynamic correlation was recovered by multireference configuration interaction or multireference perturbation theory. For molecules not having equivalent atoms, all methods led to comparable and accurate transition energies. For molecules with equivalent atoms, the most accurate results were obtained by multireference perturbation theory. Scalar relativistic effects were accounted for using the Douglas-Kroll-Hess Hamiltonian.

7 CFR 51.2542 - U.S. Artificially Opened.

Code of Federal Regulations, 2010 CFR

2010-01-01

... STANDARDS) United States Standards for Grades of Pistachio Nuts in the Shell § 51.2542 U.S. Artificially Opened. “U.S. Artificially Opened” consists of artificially opened pistachio nuts in the shell which meet...

Hydration energies and structures of alkaline earth metal ions, M2+(H2O)n, n = 5-7, M = Mg, Ca, Sr, and Ba.

PubMed

Rodriguez-Cruz, S E; Jockusch, R A; Williams, E R

1999-09-29

The evaporation of water from hydrated alkaline earth metal ions, produced by electrospray ionization, was studied in a Fourier transform mass spectrometer. Zero-pressure-limit dissociation rate constants for loss of a single water molecule from the hydrated divalent metal ions, M(2+)(H(2)O)(n) (M = Mg, Ca, and Sr for n = 5-7, and M = Ba for n = 4-7), are measured as a function of temperature using blackbody infrared radiative dissociation. From these values, zero-pressure-limit Arrhenius parameters are obtained. By modeling the dissociation kinetics using a master equation formalism, threshold dissociation energies (E(o)) are determined. These reactions should have a negligible reverse activation barrier; therefore, E(o) values should be approximately equal to the binding energy or hydration enthalpy at 0 K. For the hepta- and hexahydrated ions at low temperature, binding energies follow the trend expected on the basis of ionic radii: Mg > Ca > Sr > Ba. For the hexahydrated ions at high temperature, binding energies follow the order Ca > Mg > Sr > Ba. The same order is observed for the pentahydrated ions. Collisional dissociation experiments on the tetrahydrated species result in relative dissociation rates that directly correlate with the size of the metals. These results indicate the presence of two isomers for hexahydrated magnesium ions: a low-temperature isomer in which the six water molecules are located in the first solvation shell, and a high-temperature isomer with the most likely structure corresponding to four water molecules in the inner shell and two water molecules in the second shell. These results also indicate that the pentahydrated magnesium ions have a structure with four water molecules in the first solvation shell and one in the outer shell. The dissociation kinetics for the hexa- and pentahydrated clusters of Ca(2+), Sr(2+), and Ba(2+) are consistent with structures in which all the water molecules are located in the first solvation shell.

Solvation of carbonaceous molecules by para-H2 and ortho-D2 clusters. II. Fullerenes.

PubMed

Calvo, F; Yurtsever, E

2016-08-28

The coating of various fullerenes by para-hydrogen and ortho-deuterium molecules has been computationally studied as a function of the solvent amount. Rotationally averaged interaction potentials for structureless hydrogen molecules are employed to model their interaction with neutral or charged carbonaceous dopants containing between 20 and 240 atoms, occasionally comparing different fullerenes having the same size but different shapes. The solvation energy and the size of the first solvation shell obtained from path-integral molecular dynamics simulations at 2 K show only minor influence on the dopant charge and on the possible deuteration of the solvent, although the shell size is largest for ortho-D2 coating cationic fullerenes. Nontrivial finite size effects have been found with the shell size varying non-monotonically close to its completion limit. For fullerenes embedded in large hydrogen clusters, the shell size and solvation energy both follow linear scaling with the fullerene size. The shell sizes obtained for C60 (+) and C70 (+) are close to 49 and 51, respectively, and agree with mass spectrometry experiments.

Solvation of carbonaceous molecules by para-H2 and ortho-D2 clusters. II. Fullerenes

NASA Astrophysics Data System (ADS)

Calvo, F.; Yurtsever, E.

2016-08-01

The coating of various fullerenes by para-hydrogen and ortho-deuterium molecules has been computationally studied as a function of the solvent amount. Rotationally averaged interaction potentials for structureless hydrogen molecules are employed to model their interaction with neutral or charged carbonaceous dopants containing between 20 and 240 atoms, occasionally comparing different fullerenes having the same size but different shapes. The solvation energy and the size of the first solvation shell obtained from path-integral molecular dynamics simulations at 2 K show only minor influence on the dopant charge and on the possible deuteration of the solvent, although the shell size is largest for ortho-D2 coating cationic fullerenes. Nontrivial finite size effects have been found with the shell size varying non-monotonically close to its completion limit. For fullerenes embedded in large hydrogen clusters, the shell size and solvation energy both follow linear scaling with the fullerene size. The shell sizes obtained for C 60+ and C 70+ are close to 49 and 51, respectively, and agree with mass spectrometry experiments.

Dual-Shell Fluorescent Nanoparticles for Self-Monitoring of pH-Responsive Molecule-Releasing in a Visualized Way.

PubMed

Yang, Lingang; Cui, Chuanfeng; Wang, Lingzhi; Lei, Juying; Zhang, Jinlong

2016-07-27

The rational design and controlled synthesis of a smart device with flexibly tailored response ability is all along desirable for bioapplication but long remains a considerable challenge. Here, a pH-stimulated valve system with a visualized "on-off" mode is constructed through a dual-shell fluorescence resonance energy transfer (FRET) strategy. The dual shells refer to carbon dots and fluorescent molecules embedded polymethacrylic acid (F-PMAA) layers successively coating around a SiO2 core (ca. 120 nm), which play the roles as energy donor and acceptor, respectively. The total thickness of the dual-shell in the solid composite is ca. 10 nm. The priorities of this dual-shell FRET nanovalve stem from three facts: (1) the thin shell allows the formation of efficient FRET system without chemical bonding between energy donor and acceptor; (2) the maximum emission wavelength of CD layer is tunable in the range of 400-600 nm, thus providing a flexible energy donor for a wide variety of energy acceptors; (3) the outer F-PMAA shell with a pH-sensitive swelling-shrinking (on-off) behavior functions as a valve for regulating the FRET process. As such, a sensitive and stable pH ratiometric sensor with a working pH range of 3-6 has been built by simply encapsulating pH-responsive fluorescein isothiocyanate (FITC) into PMAA; a pH-dependent swelling-shrinking shuttle carrier with a finely controllable molecule-release behavior has been further fabricated using rhodamine B isothiocyanate (RBITC) as the energy donor and model guest molecule. Significantly, the controlled releasing process is visually self-monitorable.

Structure and properties of silk from the African wild silkmoth Gonometa postica reared indoors.

PubMed

Teshome, Addis; Raina, S K; Vollrath, Fritz

2014-03-07

African wild silkmoth, Gonometa postica Walker (Lepidoptera: Lasiocampidae), were reared indoors in order to examine the influence of rearing conditions on the structure and properties of silk cocoon shells and degummed fibers by using a scanning electron microscope, an Instron tensile tester, and a thermogravimetric analyzer. The cocoons reared indoors showed inferior quality in weight, length, width, and cocoon shell ratio compared to cocoons reared outdoors. There were no differences in cocoon shell and fiber surfaces and cross sectional structures. Cocoon shells were covered with calcium oxalate crystals with few visible fibers on their surface. Degummed fibers were smooth with minimum unfractured surfaces and globular to triangular cross sections. Indoor-reared cocoon shells had a significantly higher breaking strain, while the breaking stress was higher for cocoons reared outdoors. Fibers from indoor cocoons had a significantly higher breaking stress while outdoor fibers had higher breaking strain. Thermogravimetric analysis curves showed two main thermal reactions revealing the dehydration of water molecules and ir-reversible decomposition of the crystallites in both cocoons and fibers reared indoors and outdoors. Cocoon shells underwent additional peaks of decomposition with increased temperature. The total weight loss was higher for cocoon shells and degummed fibers from indoors. Rearing conditions (temperature and relative humidity), feeding method used, changes in total life span, days to molting, and spinning might have influenced the variation in the properties observed.The ecological and commercial significances of indoor rearing of G. posticaare discussed. This is an open access paper. We use the Creative Commons Attribution 3.0 license that permits unrestricted use, provided that the paper is properly attributed.

Formation, characterization, and dynamics of onion-like carbon structures for electrical energy storage from nanodiamonds using reactive force fields

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

Ganesh, P.; Kent, P. R. C.; Mochalin, V.

We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbonnanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core of themore » nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbonnanostructure appears, with a shell-shell spacing of about ~3.4 Å for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large (~29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less

Formation, characterization and dynamics of onion like carbon structures from nanodiamonds using reactive force-fields for electrical energy storage

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

Kent, Paul R

We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less

Dielectronic recombination of the 4p and 4d open sub-shell tungsten ions

NASA Astrophysics Data System (ADS)

Li, M. J.; Fu, Y. B.; Zhang, G. D.; Zhang, Y. Z.; Dong, C. Z.; Koike, F.

2014-04-01

Dielectronic recombination rate coefficients are given theoretically for several highly charged tungsten ions. As 4p open sub-shell ions, Ga-, Ge-, As-, Br-, Kr-like ions are considered. Rb-like ion is further considered as a 4d open sub-shell ion. Theoretical calculations are carried out using a relativistic atomic code FAC. The effect of configuration interaction is taking into account. Inner-shell electron excitations play a significant role for the dielectronic recombination process. Simple analytical formulae are given for the total rate coefficients by fitting to the presently obtained numerical results.

Constrained-pairing mean-field theory. IV. Inclusion of corresponding pair constraints and connection to unrestricted Hartree-Fock theory.

PubMed

Tsuchimochi, Takashi; Henderson, Thomas M; Scuseria, Gustavo E; Savin, Andreas

2010-10-07

Our previously developed constrained-pairing mean-field theory (CPMFT) is shown to map onto an unrestricted Hartree-Fock (UHF) type method if one imposes a corresponding pair constraint to the correlation problem that forces occupation numbers to occur in pairs adding to one. In this new version, CPMFT has all the advantages of standard independent particle models (orbitals and orbital energies, to mention a few), yet unlike UHF, it can dissociate polyatomic molecules to the correct ground-state restricted open-shell Hartree-Fock atoms or fragments.

Response to ``Comment on `Excitations in photoactive molecules from quantum Monte Carlo' '' [J. Chem. Phys. 122, 087101 (2005)

NASA Astrophysics Data System (ADS)

Filippi, Claudia; Buda, Francesco

2005-02-01

We find that regions of the excited state potential energy surface of formaldimine, which are accessible from the Franck-Condon configuration, are incorrectly described by the restricted open-shell Kohn-Sham (ROKS) approach. In these regions, the deviations of the ROKS energies from the time-dependent density functional theory results are not a simple shift. Contrary to what is argued in the Comment by Doltsinis and Fink [J. Chem. Phys.XX, XXX (2004)], these differences can play a role in the excited state molecular dynamics of formaldimine at finite temperature.

Time-resolved inner-shell photoelectron spectroscopy: From a bound molecule to an isolated atom

NASA Astrophysics Data System (ADS)

Brauße, Felix; Goldsztejn, Gildas; Amini, Kasra; Boll, Rebecca; Bari, Sadia; Bomme, Cédric; Brouard, Mark; Burt, Michael; de Miranda, Barbara Cunha; Düsterer, Stefan; Erk, Benjamin; Géléoc, Marie; Geneaux, Romain; Gentleman, Alexander S.; Guillemin, Renaud; Ismail, Iyas; Johnsson, Per; Journel, Loïc; Kierspel, Thomas; Köckert, Hansjochen; Küpper, Jochen; Lablanquie, Pascal; Lahl, Jan; Lee, Jason W. L.; Mackenzie, Stuart R.; Maclot, Sylvain; Manschwetus, Bastian; Mereshchenko, Andrey S.; Mullins, Terence; Olshin, Pavel K.; Palaudoux, Jérôme; Patchkovskii, Serguei; Penent, Francis; Piancastelli, Maria Novella; Rompotis, Dimitrios; Ruchon, Thierry; Rudenko, Artem; Savelyev, Evgeny; Schirmel, Nora; Techert, Simone; Travnikova, Oksana; Trippel, Sebastian; Underwood, Jonathan G.; Vallance, Claire; Wiese, Joss; Simon, Marc; Holland, David M. P.; Marchenko, Tatiana; Rouzée, Arnaud; Rolles, Daniel

2018-04-01

Due to its element and site specificity, inner-shell photoelectron spectroscopy is a widely used technique to probe the chemical structure of matter. Here, we show that time-resolved inner-shell photoelectron spectroscopy can be employed to observe ultrafast chemical reactions and the electronic response to the nuclear motion with high sensitivity. The ultraviolet dissociation of iodomethane (CH3I ) is investigated by ionization above the iodine 4 d edge, using time-resolved inner-shell photoelectron and photoion spectroscopy. The dynamics observed in the photoelectron spectra appear earlier and are faster than those seen in the iodine fragments. The experimental results are interpreted using crystal-field and spin-orbit configuration interaction calculations, and demonstrate that time-resolved inner-shell photoelectron spectroscopy is a powerful tool to directly track ultrafast structural and electronic transformations in gas-phase molecules.

Assessing open-system behavior of 14C in terrestrial gastropod shells

USGS Publications Warehouse

Rech, Jason A.; Pigati, Jeffrey S.; Lehmann, Sophie B.; McGimpsey, Chelsea N.; Grimley, David A.; Nekola, Jeffrey C.

2011-01-01

In order to assess open-system behavior of radiocarbon in fossil gastropod shells, we measured the 14C activity on 10 aliquots of shell material recovered from Illinoian (~190-130 ka) and pre-Illinoian (~800 ka) loess and lacustrine deposits in the Midwestern USA. Eight of the 10 aliquots yielded measurable 14C activities that ranged from 0.25 to 0.53 percent modern carbon (pMC), corresponding to apparent 14C ages between 48.2 and 42.1 ka. This small level of open-system behavior is common in many materials that are used for 14C dating (e.g. charcoal), and typically sets the upper practical limit of the technique. Two aliquots of gastropod shells from the Illinoian-aged Petersburg Silt (Petersburg Section) in central Illinois, USA, however, yielded elevated 14C activities of 1.26 and 1.71 pMC, which correspond to apparent 14C ages of 35.1 and 32.7 ka. Together, these results suggest that while many fossil gastropods shells may not suffer from major (>1%) open-system problems, this is not always the case. We then examined the mineralogy, trace element chemistry, and physical characteristics of a suite of fossil and modern gastropod shells to identify the source of contamination in the Petersburg shells and assess the effectiveness of these screening techniques at identifying samples suitable for 14C dating. Mineralogical (XRD) and trace element analyses were inconclusive, which suggests that these techniques are not suitable for assessing open-system behavior in terrestrial gastropod shells. Analysis with scanning electron microscopy (SEM), however, identified secondary mineralization (calcium carbonate) primarily within the inner whorls of the Petersburg shells. This indicates that SEM examination, or possibly standard microscope examination, of the interior of gastropod shells should be used when selecting fossil gastropod shells for 14C dating.

Assessing open-system behavior of 14C in terrestrial gastropod shells

USGS Publications Warehouse

Rech, J.A.; Pigati, J.S.; Lehmann, S.B.; McGimpsey, C.N.; Grimley, D.A.; Nekola, J.C.

2011-01-01

In order to assess open-system behavior of radiocarbon in fossil gastropod shells, we measured the 14C activity on 10 aliquots of shell material recovered from Illinoian (~190-130 ka) and pre-Illinoian (~800 ka) loess and lacustrine deposits in the Midwestern USA. Eight of the 10 aliquots yielded measurable 14C activities that ranged from 0.25 to 0.53 percent modern carbon (pMC), corresponding to apparent 14C ages between 48.2 and 42.1 ka. This small level of open-system behavior is common in many materials that are used for 14C dating (e.g. charcoal), and typically sets the upper practical limit of the technique. Two aliquots of gastropod shells from the Illinoian-aged Petersburg Silt (Petersburg Section) in central Illinois, USA, however, yielded elevated 14C activities of 1.26 and 1.71 pMC, which correspond to apparent 14C ages of 35.1 and 32.7 ka. Together, these results suggest that while many fossil gastropods shells may not suffer from major (>1%) open-system problems, this is not always the case. We then examined the mineralogy, trace element chemistry, and physical characteristics of a suite of fossil and modern gastropod shells to identify the source of contamination in the Petersburg shells and assess the effectiveness of these screening techniques at identifying samples suitable for 14C dating. Mineralogical (XRD) and trace element analyses were inconclusive, which suggests that these techniques are not suitable for assessing open-system behavior in terrestrial gastropod shells. Analysis with scanning electron microscopy (SEM), however, identified secondary mineralization (calcium carbonate) primarily within the inner whorls of the Petersburg shells. This indicates that SEM examination, or possibly standard microscope examination, of the interior of gastropod shells should be used when selecting fossil gastropod shells for 14C dating. ?? 2011 by the Arizona Board of Regents on behalf of the University of Arizona.

Many-molecule encapsulation by an icosahedral shell

PubMed Central

Perlmutter, Jason D; Mohajerani, Farzaneh; Hagan, Michael F

2016-01-01

We computationally study how an icosahedral shell assembles around hundreds of molecules. Such a process occurs during the formation of the carboxysome, a bacterial microcompartment that assembles around many copies of the enzymes ribulose 1,5-bisphosphate carboxylase/ oxygenase and carbonic anhydrase to facilitate carbon fixation in cyanobacteria. Our simulations identify two classes of assembly pathways leading to encapsulation of many-molecule cargoes. In one, shell assembly proceeds concomitantly with cargo condensation. In the other, the cargo first forms a dense globule; then, shell proteins assemble around and bud from the condensed cargo complex. Although the model is simplified, the simulations predict intermediates and closure mechanisms not accessible in experiments, and show how assembly can be tuned between these two pathways by modulating protein interactions. In addition to elucidating assembly pathways and critical control parameters for microcompartment assembly, our results may guide the reengineering of viruses as nanoreactors that self-assemble around their reactants. DOI: http://dx.doi.org/10.7554/eLife.14078.001 PMID:27166515

Inner-shell excitation and ionic fragmentation of molecules

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

Hitchcock, A.P.; Tyliszczak, T.; Cavell, R.G.

1997-04-01

Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can revealmore » cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.« less

Proposed Ancestors of Phage Nucleic Acid Packaging Motors (and Cells)

PubMed Central

Serwer, Philip

2011-01-01

I present a hypothesis that begins with the proposal that abiotic ancestors of phage RNA and DNA packaging systems (and cells) include mobile shells with an internal, molecule-transporting cavity. The foundations of this hypothesis include the conjecture that current nucleic acid packaging systems have imprints from abiotic ancestors. The abiotic shells (1) initially imbibe and later also bind and transport organic molecules, thereby providing a means for producing molecular interactions that are links in the chain of events that produces ancestors to the first molecules that are both information carrying and enzymatically active, and (2) are subsequently scaffolds on which proteins assemble to form ancestors common to both shells of viral capsids and cell membranes. Emergence of cells occurs via aggregation and merger of shells and internal contents. The hypothesis continues by using proposed imprints of abiotic and biotic ancestors to deduce an ancestral thermal ratchet-based DNA packaging motor that subsequently evolves to integrate a DNA packaging ATPase that provides a power stroke. PMID:21994778

Open-Shell-Character-Based Molecular Design Principles: Applications to Nonlinear Optics and Singlet Fission.

PubMed

Nakano, Masayoshi

2017-01-01

Open-shell character, e. g., diradical character, is a quantum chemically well-defined quantity in ground-state molecular systems, which is not an observable but can quantify the degree of effective bond weakness in the chemical sense or electron correlation strength in the physical sense. Because this quantity also correlates to specific excited states, physicochemical properties concerned with those states are expected to strongly correlate to the open-shell character. This feature enables us to open a new path to revealing the mechanism of these properties as well as to realizing new design principles for efficient functional molecular systems. This account explains the open-shell-character-based molecular design principles and introduces their applications to the rational design of highly efficient nonlinear optical and singlet fission molecular systems. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Communication: Spin densities within a unitary group based spin-adapted open-shell coupled-cluster theory: Analytic evaluation of isotropic hyperfine-coupling constants for the combinatoric open-shell coupled-cluster scheme

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

Datta, Dipayan, E-mail: datta.dipayan@gmail.com; Gauss, Jürgen, E-mail: gauss@uni-mainz.de

We report analytical calculations of isotropic hyperfine-coupling constants in radicals using a spin-adapted open-shell coupled-cluster theory, namely, the unitary group based combinatoric open-shell coupled-cluster (COSCC) approach within the singles and doubles approximation. A scheme for the evaluation of the one-particle spin-density matrix required in these calculations is outlined within the spin-free formulation of the COSCC approach. In this scheme, the one-particle spin-density matrix for an open-shell state with spin S and M{sub S} = + S is expressed in terms of the one- and two-particle spin-free (charge) density matrices obtained from the Lagrangian formulation that is used for calculating themore » analytic first derivatives of the energy. Benchmark calculations are presented for NO, NCO, CH{sub 2}CN, and two conjugated π-radicals, viz., allyl and 1-pyrrolyl in order to demonstrate the performance of the proposed scheme.« less

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements

NASA Astrophysics Data System (ADS)

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-01

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N5 AO to MO transformation in contrast to the ΔCCSD method.

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements.

PubMed

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-07

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N 5 AO to MO transformation in contrast to the ΔCCSD method.

High performance of PbSe/PbS core/shell quantum dot heterojunction solar cells: short circuit current enhancement without the loss of open circuit voltage by shell thickness control.

PubMed

Choi, Hyekyoung; Song, Jung Hoon; Jang, Jihoon; Mai, Xuan Dung; Kim, Sungwoo; Jeong, Sohee

2015-11-07

We fabricated heterojunction solar cells with PbSe/PbS core shell quantum dots and studied the precisely controlled PbS shell thickness dependency in terms of optical properties, electronic structure, and solar cell performances. When the PbS shell thickness increases, the short circuit current density (JSC) increases from 6.4 to 11.8 mA cm(-2) and the fill factor (FF) enhances from 30 to 49% while the open circuit voltage (VOC) remains unchanged at 0.46 V even with the decreased effective band gap. We found that the Fermi level and the valence band maximum level remain unchanged in both the PbSe core and PbSe/PbS core/shell with a less than 1 nm thick PbS shell as probed via ultraviolet photoelectron spectroscopy (UPS). The PbS shell reduces their surface trap density as confirmed by relative quantum yield measurements. Consequently, PbS shell formation on the PbSe core mitigates the trade-off relationship between the open circuit voltage and the short circuit current density. Finally, under the optimized conditions, the PbSe core with a 0.9 nm thick shell yielded a power conversion efficiency of 6.5% under AM 1.5.

Closure system

DOEpatents

Hertelendy, N.A.

1987-04-22

A pressure resistant seal for a metallic container is formed between a cylindrical portion having one end open and a cap which seals the open end of the shell. The cap is in the form of a frusto-conical flange which is inserted narrow end first into the open end of the shell and the container is sealed by means of a capping tool which pulls the flange against a die, deforming the flange and forcing the edge of the flange into the wall of the shell. 6 figs.

Closure system

DOEpatents

Hertelendy, Nicholas A [Kennewick, WA

1989-01-01

A pressure resistant seal for a metallic container is formed between a cylindrical portion having one end open and a cap which seals the open end of the shell. The cap is in the form of a frusto-conical flange which is inserted narrow end first into the open end of the shell and the container is sealed by means of a capping tool which pulls the flange against a die, deforming the flange and forcing the edge of the flange into the wall of the shell.

Closure system

DOEpatents

Hertelendy, Nicholas A.

1989-04-04

A pressure resistant seal for a metallic container is formed between a cylindrical portion having one end open and a cap which seals the open end of the shell. The cap is in the form of a frusto-conical flange which is inserted narrow end first into the open end of the shell and the container is sealed by means of a capping tool which pulls the flange against a die, deforming the flange and forcing the edge of the flange into the wall of the shell.

Hydration Energies and Structures of Alkaline Earth Metal Ions, M2+ (H2O)n, n = 5–7, M = Mg, Ca, Sr, and Ba

PubMed Central

Rodriguez-Cruz, Sandra E.; Jockusch, Rebecca A.

2005-01-01

The evaporation of water from hydrated alkaline earth metal ions, produced by electrospray ionization, was studied in a Fourier transform mass spectrometer. Zero-pressure-limit dissociation rate constants for loss of a single water molecule from the hydrated divalent metal ions, M2+(H2O)n (M = Mg, Ca, and Sr for n = 5–7, and M = Ba for n = 4–7), are measured as a function of temperature using blackbody infrared radiative dissociation. From these values, zero-pressure-limit Arrhenius parameters are obtained. By modeling the dissociation kinetics using a master equation formalism, threshold dissociation energies (Eo) are determined. These reactions should have a negligible reverse activation barrier; therefore, Eo values should be approximately equal to the binding energy or hydration enthalpy at 0 K. For the hepta- and hexahydrated ions at low temperature, binding energies follow the trend expected on the basis of ionic radii: Mg > Ca > Sr > Ba. For the hexahydrated ions at high temperature, binding energies follow the order Ca > Mg > Sr > Ba. The same order is observed for the pentahydrated ions. Collisional dissociation experiments on the tetrahydrated species result in relative dissociation rates that directly correlate with the size of the metals. These results indicate the presence of two isomers for hexahydrated magnesium ions: a low-temperature isomer in which the six water molecules are located in the first solvation shell, and a high-temperature isomer with the most likely structure corresponding to four water molecules in the inner shell and two water molecules in the second shell. These results also indicate that the pentahydrated magnesium ions have a structure with four water molecules in the first solvation shell and one in the outer shell. The dissociation kinetics for the hexa- and pentahydrated clusters of Ca2+, Sr2+, and Ba2+ are consistent with structures in which all the water molecules are located in the first solvation shell. PMID:16429612

Optical oscillator strengths of the valence-shell excitations of atoms and molecules determined by the dipole ( γ,γ) method

NASA Astrophysics Data System (ADS)

Xu, Long-Quan; Liu, Ya-Wei; Xu, Xin; Ni, Dong-Dong; Yang, Ke; Zhu, Lin-Fan

2017-07-01

The dipole (γ,γ) method, which is the inelastic X-ray scattering operated at a negligibly small momentum transfer, has been developed to determine the absolute optical oscillator strengths of the valence-shell excitations of atoms and molecules. This new method is free from the line saturation effect, and its Bethe-Born conversion factor varies much more slowly with the excitation energy than that of the dipole (e, e) method. Thus the dipole (γ,γ) method provides a reliable approach to obtain the benchmark optical oscillator strengths of the valence-shell excitations for gaseous atoms and molecules. In this paper, we give a review of the dipole (γ,γ) method and some recent measurements of absolute optical oscillator strengths of gaseous atoms and molecules. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Development of magnetic luminescent core/shell nanocomplex particles with fluorescence using Rhodamine 6G

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

Lee, Hee Uk; Song, Yoon Seok; Park, Chulhwan

2012-12-15

Graphical abstract: Display Omitted Highlights: ► A simple method was developed to synthesize Co-B/SiO{sub 2}/dye/SiO{sub 2} composite particles. ► The magnetic particle shows that highly luminescent and core/shell particles are formed. ► Such core/shell particles can be easily suspended in water. ► The magnetic particles could detect fluorescence for the application of biosensor. -- Abstract: A simple and reproducible method was developed to synthesize a novel class of Co-B/SiO{sub 2}/dye/SiO{sub 2} composite core/shell particles. Using a single cobalt core, Rhodamine 6G of organic dye molecules was entrapped in a silica shell, resulting in core/shell particles of ∼200 nm diameter. Analysesmore » using a variety of techniques such as transmission electron microscopy, X-ray photoelectron spectroscopy, vibration sample magnetometry, confocal laser scanning microscopy, and fluorescence intensity demonstrated that dye molecules were trapped inside the core/shell particles. A photoluminescence investigation showed that highly luminescent and photostable core/shell particles were formed. Such core/shell particles can be easily suspended in water. The synthesized magnetic particles could be used to detect fluorescence on glass substrate arrays for bioassay and biosensor applications.« less

Communication: Multiple-property-based diabatization for open-shell van der Waals molecules

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

Karman, Tijs; Avoird, Ad van der; Groenenboom, Gerrit C., E-mail: gerritg@theochem.ru.nl

2016-03-28

We derive a new multiple-property-based diabatization algorithm. The transformation between adiabatic and diabatic representations is determined by requiring a set of properties in both representations to be related by a similarity transformation. This set of properties is determined in the adiabatic representation by rigorous electronic structure calculations. In the diabatic representation, the same properties are determined using model diabatic states defined as products of undistorted monomer wave functions. This diabatic model is generally applicable to van der Waals molecules in arbitrary electronic states. Application to locating seams of conical intersections and collisional transfer of electronic excitation energy is demonstrated formore » O{sub 2} − O{sub 2} in low-lying excited states. Property-based diabatization for this test system included all components of the electric quadrupole tensor, orbital angular momentum, and spin-orbit coupling.« less

Nanoconfinement Effects in Catalysis

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

Kung, Harold H.

In this investigation, the unique properties that stem from the constrained environment and enforced proximity of functional groups at the active site were demonstrated for a number of systems. The first system is a nanocage structure with silicon-based, atom-thick shells and molecular-size cavities. The shell imparts the expected size exclusion for access to the interior cavity, and the confined space together with the hydrophobic shell strongly influences the stability of charged groups. One consequence is that the interior amine groups in a siloxane nanocage exhibit a shift in their protonation ability that is equivalent to about 4 pH units. Inmore » another nanocage structure designed to possess a core-shell structure in which the core periphery is decorated with carboxylic acid groups and the shell interior is populated with silanol groups, the restricted motion of the core results in limiting the stoichiometry of reaction between carboxylic acid and a Co 2CO 8 complex, which leads to formation and stabilization of Co(I) ions in the nanocage. The second designed catalytic structure is a supported, isolated, Lewis acid Sn-oxide unit derived from a (POSS)-Sn-(POSS) molecular complex (POSS = incompletely condensed silsesquioxane). The Sn center in the (POSS)-Sn-(POSS) complex is present in a tetrahedral coordination, as confirmed by single crystal x-ray crystallography and Sn NMR, and its Lewis acid character is demonstrated with its binding to amines. The retention of the tetrahedral coordination of Sn after heterogenization and mild oxidative treatment is confirmed by characterization using EXAFS, NMR, UV-vis, and DRIFT, and its Lewis acid character is confirmed by stoichiometric binding with pyridine. This Sn-catalyst is active in hydride transfer reactions as a typical solid Lewis acid. In addition, the Sn centers can also create Brønsted acidity with alcohol by binding the alcohol strongly as alkoxide and transferring the hydroxyl H to the neighboring Sn-O-Si bond. The resulting acidic silanol is active in epoxide ring opening and acetalization reactions. The open structure of the Sn center makes it accessible to larger molecules, including cellobiose which can be converted to 5-(hydroxymethyl)-furfural. The third structure is a support planted with functional group pairing of a known separation distance. Using a precursor molecule that contains a hydrolysable silyl ester bond, and making use of known chemistry to convert silanol groups into amino/pyridyl and phosphinyl groups, silica surfaces with carboxylic acid/silanol, carboxylic acid/amine, carboxylic acid/pyridine, and carboxylic acid/phosphine pairs can be constructed. The amino groups paired with carboxylic acid on such a surface is more active in the Henry reaction of 4-nitobenzaldehyde with nitromethane.« less

Sigma- versus Pi-Dimerization Modes of Triangulene.

PubMed

Mou, Zhongyu; Kertesz, Miklos

2018-04-20

We show that the diradicaloid triangulene, a graphene nano-flake molecule, can aggregate in a variety of dimerization modes. We found by density functional theory modeling a number of triangulene dimers including six doubly bonded σ-dimers in addition to the previously reported six pancake bonded π-dimer isomers. The σ-dimers display a wide range of stabilities: the interaction energy of the most stable σ-dimer is -25.17 kcal mol -1 . Besides the doubly bonded σ-dimers with closed shell ground states, we also found an open-shell singly σ-bonded diradicaloid dimer. We found an interesting isomerization route between a doubly bonded σ-dimer, a singly bonded σ-dimer with a low-lying triplet state and two π-bonded dimers with low-lying quintet states. Derivatives of triangulene, trioxo-triangulenes (TOTs) have been previously characterized experimentally. Here, we show the reasons why so far only the π-dimer but not the σ-dimer was experimentally observed for all TOTs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measuring the reactivity of a silicon-terminated probe

NASA Astrophysics Data System (ADS)

Sweetman, Adam; Stirling, Julian; Jarvis, Samuel Paul; Rahe, Philipp; Moriarty, Philip

2016-09-01

It is generally accepted that the exposed surfaces of silicon crystals are highly reactive due to the dangling bonds which protrude into the vacuum. However, surface reconstruction not only modifies the reactivity of bulk silicon crystals, but also plays a key role in determining the properties of silicon nanocrystals. In this study we probe the reactivity of silicon clusters at the end of a scanning probe tip by examining their interaction with closed-shell fullerene molecules. Counter to intuitive expectations, many silicon clusters do not react strongly with the fullerene cage, and we find that only specific highly oriented clusters have sufficient reactivity to break open the existing carbon-carbon bonds.

Second-Order Moller-Plesset Perturbation Theory for Molecular Dirac-Hartree-Fock Wave Functions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.; Arnold, James O. (Technical Monitor)

1994-01-01

Moller-Plesset perturbation theory is developed to second order for a selection of Kramers restricted Dirac-Hartree-Fock closed and open-shell reference wave functions. The open-shell wave functions considered are limited to those with no more than two electrons in open shells, but include the case of a two-configuration SCF reference. Denominator shifts are included in the style of Davidson's OPT2 method. An implementation which uses unordered integrals with labels is presented, and results are given for a few test cases.

Computational investigation of longitudinal diffusion, eddy dispersion, and trans-particle mass transfer in bulk, random packings of core-shell particles with varied shell thickness and shell diffusion coefficient.

PubMed

Daneyko, Anton; Hlushkou, Dzmitry; Baranau, Vasili; Khirevich, Siarhei; Seidel-Morgenstern, Andreas; Tallarek, Ulrich

2015-08-14

In recent years, chromatographic columns packed with core-shell particles have been widely used for efficient and fast separations at comparatively low operating pressure. However, the influence of the porous shell properties on the mass transfer kinetics in core-shell packings is still not fully understood. We report on results obtained with a modeling approach to simulate three-dimensional advective-diffusive transport in bulk random packings of monosized core-shell particles, covering a range of reduced mobile phase flow velocities from 0.5 up to 1000. The impact of the effective diffusivity of analyte molecules in the porous shell and the shell thickness on the resulting plate height was investigated. An extension of Giddings' theory of coupled eddy dispersion to account for retention of analyte molecules due to stagnant regions in porous shells with zero mobile phase flow velocity is presented. The plate height equation involving a modified eddy dispersion term excellently describes simulated data obtained for particle-packings with varied shell thickness and shell diffusion coefficient. It is confirmed that the model of trans-particle mass transfer resistance of core-shell particles by Kaczmarski and Guiochon [42] is applicable up to a constant factor. We analyze individual contributions to the plate height from different mass transfer mechanisms in dependence of the shell parameters. The simulations demonstrate that a reduction of plate height in packings of core-shell relative to fully porous particles arises mainly due to reduced trans-particle mass transfer resistance and transchannel eddy dispersion. Copyright © 2015 Elsevier B.V. All rights reserved.

Multicompartmental Microcapsules with Orthogonal Programmable Two-Way Sequencing of Hydrophobic and Hydrophilic Cargo Release.

PubMed

Xu, Weinan; Ledin, Petr A; Iatridi, Zacharoula; Tsitsilianis, Constantinos; Tsukruk, Vladimir V

2016-04-11

Multicompartmental responsive microstructures with the capability for the pre-programmed sequential release of multiple target molecules of opposite solubility (hydrophobic and hydrophilic) in a controlled manner have been fabricated. Star block copolymers with dual-responsive blocks (temperature for poly(N-isopropylacrylamide) chains and pH for poly(acrylic acid) and poly(2-vinylpyridine) arms) and unimolecular micellar structures serve as nanocarriers for hydrophobic molecules in the microcapsule shell. The interior of the microcapsule can be loaded with water-soluble hydrophilic macromolecules. For these dual-loaded microcapsules, a programmable and sequential release of hydrophobic and hydrophilic molecules from the shell and core, respectively, can be triggered independently by temperature and pH variations. These stimuli affect the hydrophobicity and chain conformation of the star block copolymers to initiate out-of-shell release (elevated temperature), or change the overall star conformation and interlayer interactions to trigger increased permeability of the shell and out-of-core release (pH). Reversing stimulus order completely alters the release process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Global molecular identification from graphs. Neutral and ionized main-group diatomic molecules.

PubMed

James, Bryan; Caviness, Ken; Geach, Jonathan; Walters, Chris; Hefferlin, Ray

2002-01-01

Diophantine equations and inequalities are presented for main-group closed-shell diatomic molecules. Specifying various bond types (covalent, dative, ionic, van der Waals) and multiplicities, it becomes possible to identify all possible molecules. While many of the identified species are probably unstable under normal conditions, they are interesting and present a challenge for computational or experimental analysis. Ionized molecules with net charges of -1, 1, and 2 are also identified. The analysis applies to molecules with atoms from periods 2 and 3 but can be generalized by substituting isovalent atoms. When closed-shell neutral diatomics are positioned in the chemical space (with axes enumerating the numbers of valence electrons of the free atoms), it is seen that they lie on a few parallel isoelectronic series.

Shell extracts of the edible mussel and oyster induce an enhancement of the catabolic pathway of human skin fibroblasts, in vitro.

PubMed

Latire, Thomas; Legendre, Florence; Bouyoucef, Mouloud; Marin, Frédéric; Carreiras, Franck; Rigot-Jolivet, Muriel; Lebel, Jean-Marc; Galéra, Philippe; Serpentini, Antoine

2017-10-01

Mollusc shells are composed of more than 95% calcium carbonate and less than 5% organic matrix consisting mostly of proteins, glycoproteins and polysaccharides. In this study, we investigated the effects of matrix macromolecular components extracted from the shells of two edible molluscs of economic interest, i.e., the blue mussel Mytilus edulis and the Pacific oyster Crassostrea gigas. The potential biological activities of these organic molecules were analysed on human dermal fibroblasts in primary culture. Our results demonstrate that shell extracts of the two studied molluscs modulate the metabolic activities of the cells. In addition, the extracts caused a decrease of type I collagen and a concomitant increase of active MMP-1, both at the mRNA and the protein levels. Therefore, our results suggest that shell extracts from M. edulis and C. gigas contain molecules that promote the catabolic pathway of human dermal fibroblasts. This work emphasises the potential use of these shell matrices in the context of anti-fibrotic strategies, particularly against scleroderma. More generally, it stresses the usefulness to valorise bivalve shells that are coproducts of shellfish farming activity.

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory

NASA Astrophysics Data System (ADS)

Bozkaya, Uǧur

2013-09-01

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory (OMP3) [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)], 10.1063/1.3665134 are presented. The OMP3 method is applied to problematic chemical systems with challenging electronic structures. The performance of the OMP3 method is compared with those of canonical second-order Møller-Plesset perturbation theory (MP2), third-order Møller-Plesset perturbation theory (MP3), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] for investigating equilibrium geometries, vibrational frequencies, and open-shell reaction energies. For bond lengths, the performance of OMP3 is in between those of MP3 and CCSD. For harmonic vibrational frequencies, the OMP3 method significantly eliminates the singularities arising from the abnormal response contributions observed for MP3 in case of symmetry-breaking problems, and provides noticeably improved vibrational frequencies for open-shell molecules. For open-shell reaction energies, OMP3 exhibits a better performance than MP3 and CCSD as in case of barrier heights and radical stabilization energies. As discussed in previous studies, the OMP3 method is several times faster than CCSD in energy computations. Further, in analytic gradient computations for the CCSD method one needs to solve λ-amplitude equations, however for OMP3 one does not since λ _{ab}^{ij(1)} = t_{ij}^{ab(1)} and λ _{ab}^{ij(2)} = t_{ij}^{ab(2)}. Additionally, one needs to solve orbital Z-vector equations for CCSD, but for OMP3 orbital response contributions are zero owing to the stationary property of OMP3. Overall, for analytic gradient computations the OMP3 method is several times less expensive than CCSD (roughly ˜4-6 times). Considering the balance of computational cost and accuracy we conclude that the OMP3 method emerges as a very useful tool for the study of electronically challenging chemical systems.

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory.

PubMed

Bozkaya, Uğur

2013-09-14

Analytic energy gradients for the orbital-optimized third-order Møller-Plesset perturbation theory (OMP3) [U. Bozkaya, J. Chem. Phys. 135, 224103 (2011)] are presented. The OMP3 method is applied to problematic chemical systems with challenging electronic structures. The performance of the OMP3 method is compared with those of canonical second-order Møller-Plesset perturbation theory (MP2), third-order Møller-Plesset perturbation theory (MP3), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] for investigating equilibrium geometries, vibrational frequencies, and open-shell reaction energies. For bond lengths, the performance of OMP3 is in between those of MP3 and CCSD. For harmonic vibrational frequencies, the OMP3 method significantly eliminates the singularities arising from the abnormal response contributions observed for MP3 in case of symmetry-breaking problems, and provides noticeably improved vibrational frequencies for open-shell molecules. For open-shell reaction energies, OMP3 exhibits a better performance than MP3 and CCSD as in case of barrier heights and radical stabilization energies. As discussed in previous studies, the OMP3 method is several times faster than CCSD in energy computations. Further, in analytic gradient computations for the CCSD method one needs to solve λ-amplitude equations, however for OMP3 one does not since λ(ab)(ij(1))=t(ij)(ab(1)) and λ(ab)(ij(2))=t(ij)(ab(2)). Additionally, one needs to solve orbital Z-vector equations for CCSD, but for OMP3 orbital response contributions are zero owing to the stationary property of OMP3. Overall, for analytic gradient computations the OMP3 method is several times less expensive than CCSD (roughly ~4-6 times). Considering the balance of computational cost and accuracy we conclude that the OMP3 method emerges as a very useful tool for the study of electronically challenging chemical systems.

Incorporation of the TIP4P water model into a continuum solvent for computing solvation free energy

NASA Astrophysics Data System (ADS)

Yang, Pei-Kun

2014-10-01

The continuum solvent model is one of the commonly used strategies to compute solvation free energy especially for large-scale conformational transitions such as protein folding or to calculate the binding affinity of protein-protein/ligand interactions. However, the dielectric polarization for computing solvation free energy from the continuum solvent is different than that obtained from molecular dynamic simulations. To mimic the dielectric polarization surrounding a solute in molecular dynamic simulations, the first-shell water molecules was modeled using a charge distribution of TIP4P in a hard sphere; the time-averaged charge distribution from the first-shell water molecules were estimated based on the coordination number of the solute, and the orientation distribution of the first-shell waters and the intermediate water molecules were treated as that of a bulk solvent. Based on this strategy, an equation describing the solvation free energy of ions was derived.

Influence of Electrostatics on Small Molecule Flux through a Protein Nanoreactor.

PubMed

Glasgow, Jeff E; Asensio, Michael A; Jakobson, Christopher M; Francis, Matthew B; Tullman-Ercek, Danielle

2015-09-18

Nature uses protein compartmentalization to great effect for control over enzymatic pathways, and the strategy has great promise for synthetic biology. In particular, encapsulation in nanometer-sized containers to create nanoreactors has the potential to elicit interesting, unexplored effects resulting from deviations from well-understood bulk processes. Self-assembled protein shells for encapsulation are especially desirable for their uniform structures and ease of perturbation through genetic mutation. Here, we use the MS2 capsid, a well-defined porous 27 nm protein shell, as an enzymatic nanoreactor to explore pore-structure effects on substrate and product flux during the catalyzed reaction. Our results suggest that the shell can influence the enzymatic reaction based on charge repulsion between small molecules and point mutations around the pore structure. These findings also lend support to the hypothesis that protein compartments modulate the transport of small molecules and thus influence metabolic reactions and catalysis in vitro.

Myosin-induced volume increase of the hyper-mobile water surrounding actin filaments.

PubMed

Suzuki, Makoto; Kabir, Syed Rashel; Siddique, Md Shahjahan Parvez; Nazia, Umme Salma; Miyazaki, Takashi; Kodama, Takao

2004-09-10

Microwave dielectric spectroscopy can measure the rotational mobility of water molecules that hydrate proteins and the hydration-shell volume. Using this technique, we have recently shown that apart from typical hydrating water molecules with lowered mobility there are other water molecules around the actin filaments (F-actin) which have a much higher mobility than that of bulk water [Biophys. J. 85 (2003) 3154]. We report here that the volume of this water component (hyper-mobile water) markedly increases without significant change of the volume of the ordinary hydration shell when the myosin motor-domain (S1, myosin subfragment-1) binds to F-actin. No hyper-mobile component was found in the hydration shell of S1 itself. The present results strongly suggest that the solvent space around S1 bound to F-actin is diffusionally asymmetric, which supports our model of force generation by actomyosin proposed previously [op. cit.].

Structure and dynamics of phosphate ion in aqueous solution: an ab initio QMCF MD study.

PubMed

Pribil, Andreas B; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M

2008-11-15

A simulation of phosphate in aqueous solution was carried out employing the new QMCF MD approach which offers the possibility to investigate composite systems with the accuracy of a QMMM method but without the time consuming creation of solute-solvent potential functions. The data of the simulations give a clear picture of the hydration shells of the phosphate anion. The first shell consists of 13 water molecules and each oxygen of the phosphate forms in average three hydrogens bonds to different solvent molecules. Several structural parameters such as radial distribution functions and coordination number distributions allow to fully characterize the embedding of the highly charged phosphate ion in the solvent water. The dynamics of the hydration structure of phosphate are described by mean residence times of the solvent molecules in the first hydration shell and the water exchange rate. 2008 Wiley Periodicals, Inc.

Multi-orbital non-crossing approximation from maximally localized Wannier functions: the Kondo signature of copper phthalocyanine on Ag(100).

PubMed

Korytár, Richard; Lorente, Nicolás

2011-09-07

We have developed a multi-orbital approach to compute the electronic structure of a quantum impurity using the non-crossing approximation. The calculation starts with a mean-field evaluation of the system's electronic structure using a standard quantum chemistry code; here we use density functional theory (DFT). We transformed the one-electron structure into an impurity Hamiltonian by using maximally localized Wannier functions. Hence, we have developed a method to study the Kondo effect in systems based on an initial one-electron calculation. We have applied our methodology to a copper phthalocyanine molecule chemisorbed on Ag(100), and we have described its spectral function for three different cases where the molecule presents a single spin or two spins with ferro- and anti-ferromagnetic exchange couplings. We find that the use of broken-symmetry mean-field theories such as Kohn-Sham DFT cannot deal with the complexity of the spin of open-shell molecules on metal surfaces and extra modeling is needed. © 2011 IOP Publishing Ltd

Solvation structure of the halides from x-ray absorption spectroscopy

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

Antalek, Matthew; Hedman, Britt; Sarangi, Ritimukta, E-mail: ritis@slac.stanford.edu

2016-07-28

Three-dimensional models for the aqueous solvation structures of chloride, bromide, and iodide are reported. K-edge extended X-ray absorption fine structure (EXAFS) and Minuit X-ray absorption near edge (MXAN) analyses found well-defined single shell solvation spheres for bromide and iodide. However, dissolved chloride proved structurally distinct, with two solvation shells needed to explain its strikingly different X-ray absorption near edge structure (XANES) spectrum. Final solvation models were as follows: iodide, 8 water molecules at 3.60 ± 0.13 Å and bromide, 8 water molecules at 3.40 ± 0.14 Å, while chloride solvation included 7 water molecules at 3.15 ± 0.10 Å, andmore » a second shell of 7 water molecules at 4.14 ± 0.30 Å. Each of the three derived solvation shells is approximately uniformly disposed about the halides, with no global asymmetry. Time-dependent density functional theory calculations simulating the chloride XANES spectra following from alternative solvation spheres revealed surprising sensitivity of the electronic state to 6-, 7-, or 8-coordination, implying a strongly bounded phase space for the correct structure during an MXAN fit. MXAN analysis further showed that the asymmetric solvation predicted from molecular dynamics simulations using halide polarization can play no significant part in bulk solvation. Classical molecular dynamics used to explore chloride solvation found a 7-water solvation shell at 3.12 (−0.04/+0.3) Å, supporting the experimental result. These experiments provide the first fully three-dimensional structures presenting to atomic resolution the aqueous solvation spheres of the larger halide ions.« less

The synthesis of four-layer gold-silver-polymer-silver core-shell nanomushroom with inbuilt Raman molecule for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Jiang, Tao; Wang, Xiaolong; Zhou, Jun

2017-12-01

A facial two-step reduction method was proposed to synthesize four-layer gold-silver-polymer-silver (Au@Ag@PSPAA@Ag) core-shell nanomushrooms (NMs) with inbuilt Raman molecule. The surface-enhanced Raman scattering (SERS) intensity of 4MBA adhered on the surface of Au core gradually increased with the modification of middle Ag shell and then Ag mushroom cap due to the formation of two kinds of ultra-small interior nanogap. Compared with the initial Au nanoparticles, the SERS enhancement ratio of the Au@Ag@PSPAA@Ag NMs approached to nearly 40. The novel core-shell NMs also exhibited homogeneous SERS signals for only one sample and reproducible signals for 10 different samples, certified by the low relative standard deviation values of less than 10% and 15% for the character peaks of 4-mercaptobenzoic acid, respectively. Such a novel four-layer core-shell nanostructure with reliable SERS performance has great potential application in quantitative SERS-based immunoassay.

Core-shell biopolymer nanoparticle delivery systems: synthesis and characterization of curcumin fortified zein-pectin nanoparticles.

PubMed

Hu, Kun; Huang, Xiaoxia; Gao, Yongqing; Huang, Xulin; Xiao, Hang; McClements, David Julian

2015-09-01

Biopolymer core-shell nanoparticles were fabricated using a hydrophobic protein (zein) as the core and a hydrophilic polysaccharide (pectin) as the shell. Particles were prepared by coating cationic zein nanoparticles with anionic pectin molecules using electrostatic deposition (pH 4). The core-shell nanoparticles were fortified with curcumin (a hydrophobic bioactive molecule) at a high loading efficiency (>86%). The resulting nanoparticles were spherical, relatively small (diameter ≈ 250 nm), and had a narrow size distribution (polydispersity index ≈ 0.24). The encapsulated curcumin was in an amorphous (rather than crystalline form) as detected by differential scanning calorimetry (DSC). Fourier transform infrared (FTIR) and Raman spectra indicated that the encapsulated curcumin interacted with zein mainly through hydrophobic interactions. The nanoparticles were converted into a powdered form that had good water-dispersibility. These core-shell biopolymer nanoparticles could be useful for incorporating curcumin into functional foods and beverages, as well as dietary supplements and pharmaceutical products. Copyright © 2015 Elsevier Ltd. All rights reserved.

TMAO and urea in the hydration shell of the protein SNase.

PubMed

Smolin, Nikolai; Voloshin, Vladimir P; Anikeenko, Alexey V; Geiger, Alfons; Winter, Roland; Medvedev, Nikolai N

2017-03-01

We performed all-atom MD simulations of the protein SNase in aqueous solution and in the presence of two major osmolytes, trimethylamine-N-oxide (TMAO) and urea, as cosolvents at various concentrations and compositions and at different pressures and temperatures. The distributions of the cosolvent molecules and their orientation in the surroundings of the protein were analyzed in great detail. The distribution of urea is largely conserved near the protein. It varies little with pressure and temperature, and does practically not depend on the addition of TMAO. The slight decrease with temperature of the number of urea molecules that are in contact with the SNase molecule is consistent with the view that the interaction of the protein with urea is mainly of enthalpic nature. Most of the TMAO molecules tend to be oriented to the protein by its methyl groups, a small amount of these molecules contact the protein by its oxygen, forming hydrogen bonds with the protein, only. Unlike urea, the fraction of TMAO in the hydration shell of SNase slightly increases with temperature (a signature of a prevailing hydrophobic interaction between TMAO and SNase), and decreases significantly upon the addition of urea. This behavior reflects the diverse nature of the interaction of the two osmolytes with the protein. Using the Voronoi volume of the atoms of the solvent molecules (water, urea, TMAO), we compared the fraction of the volume occupied by a given type of solvent molecule in the hydration shell and in the bulk solvent. The volume fraction of urea in the hydration shell is more than two times larger than in the bulk, whereas the volume fraction of TMAO in the hydration shell is only slightly larger in the binary solvent (TMAO + water) and becomes even less than in the bulk in the ternary solvent (TMAO + water + urea). Thus, TMAO tends to be excluded from the hydration shell of the protein. The behavior of the two cosolvents in the vicinity of the protein does not change much with pressure (from 1 to 5000 bar) and temperature (from 280 to 330 K). This is also in line with the conception of the "osmophobic effect" of TMAO to protect proteins from denaturation also at harsh environmental conditions. We also calculated the volumetric parameters of SNase and found that the cosolvents have a small but significant effect on the apparent volume and its contributions, i.e. the intrinsic, molecular and thermal volumes.

Simultaneous tracking of drug molecules and carriers using aptamer-functionalized fluorescent superstable gold nanorod-carbon nanocapsules during thermo-chemotherapy

NASA Astrophysics Data System (ADS)

Wang, Xue-Wei; Gao, Wei; Fan, Huanhuan; Ding, Ding; Lai, Xiao-Fang; Zou, Yu-Xiu; Chen, Long; Chen, Zhuo; Tan, Weihong

2016-04-01

Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and therapy. Moreover, such a stable and intrinsic fluorescence effect of the AuNR@carbon enabled simultaneous tracking of released therapeutic molecules and nanocarriers under thermo-chemotherapy. The AuNR@carbons had high surface areas and stable shells, as well as unique optical and photothermal properties, making them promising nanostructures for biomedical applications.Controlling and monitoring the drug delivery process is critical to its intended therapeutic function. Many nanocarrier systems for drug delivery have been successfully developed. However, biocompatibility, stability, and simultaneously tracing drugs and nanocarriers present significant limitations. Herein, we have fabricated a multifunctional nanocomposite by coating the gold nanorod (AuNR) with a biocompatible, superstable and fluorescent carbon layer, obtaining the AuNR@carbon core-shell nanocapsule. In this system, the carbon shell, originally obtained in aqueous glucose solutions and, therefore, biocompatible in physiological environments, could be simply loaded with cell-specific aptamers and therapeutic molecules through π-π interactions, a useful tool for cancer-targeted cellular imaging and therapy. Moreover, such a stable and intrinsic fluorescence effect of the AuNR@carbon enabled simultaneous tracking of released therapeutic molecules and nanocarriers under thermo-chemotherapy. The AuNR@carbons had high surface areas and stable shells, as well as unique optical and photothermal properties, making them promising nanostructures for biomedical applications. Electronic supplementary information (ESI) available: Experimental details and characterization data for all new compounds. See DOI: 10.1039/c6nr00369a

Teaching Valence Shell Electron Pair Repulsion (VSEPR) Theory

ERIC Educational Resources Information Center

Talbot, Christopher; Neo, Choo Tong

2013-01-01

This "Science Note" looks at the way that the shapes of simple molecules can be explained in terms of the number of electron pairs in the valence shell of the central atom. This theory is formally known as valence shell electron pair repulsion (VSEPR) theory. The article explains the preferred shape of chlorine trifluoride (ClF3),…

Water Dynamics in the Hydration Shells of Biomolecules

PubMed Central

2017-01-01

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

First-principle interaction potentials for metastable He(3S) and Ne(3P) with closed-shell molecules: Application to Penning-ionizing systems

NASA Astrophysics Data System (ADS)

Hapka, Michał; Chałasiński, Grzegorz; Kłos, Jacek; Żuchowski, Piotr S.

2013-07-01

We present new interaction potential curves, calculated from first-principles, for the He(3S, 1s12s1)⋯H2 and He(3S)⋯Ar systems, relevant in recent Penning ionization experiments of Henson et al. [Science 338, 234 (2012), 10.1126/science.1229141]. Two different approaches were applied: supermolecular using coupled cluster (CC) theory and perturbational within symmetry-adapted perturbation theory (SAPT). Both methods gave consistent results, and the potentials were used to study the elastic scattering and determine the positions of shape resonances for low kinetic energy (up to 1 meV). We found a good agreement with the experiment. In addition, we investigated two other dimers composed of metastable Ne (3P, 2p53s1) and ground state He and Ar atoms. For the Ne(3P)⋯He system, a good agreement between CC and SAPT approaches was obtained. The Ne(3P)⋯Ar dimer was described only with SAPT, as CC gave divergent results. Ne* systems exhibit extremely small electronic orbital angular momentum anisotropy of the potentials. We attribute this effect to screening of an open 2p shell by a singly occupied 3s shell.

Structural and energetic properties of La3+ in water/DMSO mixtures

NASA Astrophysics Data System (ADS)

Montagna, Maria; Spezia, Riccardo; Bodo, Enrico

2017-11-01

By using molecular dynamics based on a custom polarizable force field, we have studied the solvation of La3+ in an equimolar mixture of dimethylsulfoxide (DMSO) with water. An extended structural analysis has been performed to provide a complete picture of the physical properties at the basis of the interaction of La3+ with both solvents. Through our simulations we found that, very likely, the first solvation shell in the mixture is not unlike the one found in pure water or pure DMSO and contains 9 solvent molecules. We have also found that the solvation is preferentially due to DMSO molecules with the water initially present in first shell quickly leaving to the bulk. The dehydration process of the first shell has been analyzed by both plain MD simulations and a constrained dynamics approach; the free energy profiles for the extraction of water from first shell have also been computed.

Zero-point energy effects in anion solvation shells.

PubMed

Habershon, Scott

2014-05-21

By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

Alkali-ion microsolvation with benzene molecules.

PubMed

Marques, J M C; Llanio-Trujillo, J L; Albertí, M; Aguilar, A; Pirani, F

2012-05-24

The target of this investigation is to characterize by a recently developed methodology, the main features of the first solvation shells of alkaline ions in nonpolar environments due to aromatic rings, which is of crucial relevance to understand the selectivity of several biochemical phenomena. We employ an evolutionary algorithm to obtain putative global minima of clusters formed with alkali-ions (M(+)) solvated with n benzene (Bz) molecules, i.e., M(+)-(Bz)(n). The global intermolecular interaction has been decomposed in Bz-Bz and in M(+)-Bz contributions, using a potential model based on different decompositions of the molecular polarizability of benzene. Specifically, we have studied the microsolvation of Na(+), K(+), and Cs(+) with benzene molecules. Microsolvation clusters up to n = 21 benzene molecules are involved in this work and the achieved global minimum structures are reported and discussed in detail. We observe that the number of benzene molecules allocated in the first solvation shell increases with the size of the cation, showing three molecules for Na(+) and four for both K(+) and Cs(+). The structure of this solvation shell keeps approximately unchanged as more benzene molecules are added to the cluster, which is independent of the ion. Particularly stable structures, so-called "magic numbers", arise for various nuclearities of the three alkali-ions. Strong "magic numbers" appear at n = 2, 3, and 4 for Na(+), K(+), and Cs(+), respectively. In addition, another set of weaker "magic numbers" (three per alkali-ion) are reported for larger nuclearities.

Singlet-paired coupled cluster theory for open shells

NASA Astrophysics Data System (ADS)

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

2016-06-01

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior for strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.

A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory.

PubMed

Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F; Neese, Frank

2017-04-28

The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N 6 ) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is necessary, which offers large computational savings. We show that, with the default PNO truncation parameters, approximately 99.9% of the total CCSD correlation energy is recovered for open-shell species, which is comparable to the performance of the method for closed-shells. UHF-DLPNO-CCSD shows a linear scaling behavior for closed-shell systems, while linear to quadratic scaling is obtained for open-shell systems. The largest systems we have considered contain more than 500 atoms and feature more than 10 000 basis functions with a triple-ζ quality basis set.

A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory

NASA Astrophysics Data System (ADS)

Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F.; Neese, Frank

2017-04-01

The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N6) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is necessary, which offers large computational savings. We show that, with the default PNO truncation parameters, approximately 99.9% of the total CCSD correlation energy is recovered for open-shell species, which is comparable to the performance of the method for closed-shells. UHF-DLPNO-CCSD shows a linear scaling behavior for closed-shell systems, while linear to quadratic scaling is obtained for open-shell systems. The largest systems we have considered contain more than 500 atoms and feature more than 10 000 basis functions with a triple-ζ quality basis set.

Domain model for Ca2(+)-inactivation of Ca2+ channels at low channel density.

PubMed Central

Sherman, A; Keizer, J; Rinzel, J

1990-01-01

The "shell" model for Ca2(+)-inactivation of Ca2+ channels is based on the accumulation of Ca2+ in a macroscopic shell beneath the plasma membrane. The shell is filled by Ca2+ entering through open channels, with the elevated Ca2+ concentration inactivating both open and closed channels at a rate determined by how fast the shell is filled. In cells with low channel density, the high concentration Ca2+ "shell" degenerates into a collection of nonoverlapping "domains" localized near open channels. These domains form rapidly when channels open and disappear rapidly when channels close. We use this idea to develop a "domain" model for Ca2(+)-inactivation of Ca2+ channels. In this model the kinetics of formation of an inactivated state resulting from Ca2+ binding to open channels determines the inactivation rate, a mechanism identical with that which explains single-channel recordings on rabbit-mesenteric artery Ca2+ channels (Huang Y., J. M. Quayle, J. F. Worley, N. B. Standen, and M. T. Nelson. 1989. Biophys. J. 56:1023-1028). We show that the model correctly predicts five important features of the whole-cell Ca2(+)-inactivation for mouse pancreatic beta-cells (Plants, T. D. 1988. J. Physiol. 404:731-747) and that Ca2(+)-inactivation has only minor effects on the bursting electrical activity of these cells. PMID:2174274

Multi-Shell Hollow Nanogels with Responsive Shell Permeability

PubMed Central

Schmid, Andreas J.; Dubbert, Janine; Rudov, Andrey A.; Pedersen, Jan Skov; Lindner, Peter; Karg, Matthias; Potemkin, Igor I.; Richtering, Walter

2016-01-01

We report on hollow shell-shell nanogels with two polymer shells that have different volume phase transition temperatures. By means of small angle neutron scattering (SANS) employing contrast variation and molecular dynamics (MD) simulations we show that hollow shell-shell nanocontainers are ideal systems for controlled drug delivery: The temperature responsive swelling of the inner shell controls the uptake and release, while the thermoresponsive swelling of the outer shell controls the size of the void and the colloidal stability. At temperatures between 32 °C < T < 42 °C, the hollow nanocontainers provide a significant void, which is even larger than the initial core size of the template, and they possess a high colloidal stability due to the steric stabilization of the swollen outer shell. Computer simulations showed, that temperature induced switching of the permeability of the inner shell allows for the encapsulation in and release of molecules from the cavity. PMID:26984478

The generator coordinate Dirac-Fock method for open-shell atomic systems

NASA Astrophysics Data System (ADS)

Malli, Gulzari L.; Ishikawa, Yasuyuki

1998-11-01

Recently we developed generator coordinate Dirac-Fock and Dirac-Fock-Breit methods for closed-shell systems assuming finite nucleus and have reported Dirac-Fock and Dirac-Fock-Breit energies for the atoms He through Nobelium (Z=102) [see Refs. Reference 10Reference 11Reference 12Reference 13]. In this paper, we generalize our earlier work on closed-shell systems and develop a generator coordinate Dirac-Fock method for open-shell systems. We present results for a number of representative open-shell heavy atoms (with nuclear charge Z>80) including the actinide and superheavy transactinide (with Z>103) atomic systems: Fr (Z=87), Ac (Z=89), and Lr (Z=103) to E113 (eka-thallium, Z=113). The high accuracy obtained in our open-shell Dirac-Fock calculations is similar to that of our closed-shell calculations, and we attribute it to the fact that the representation of the relativistic dynamics of an electron in a spherical ball finite nucleus near the origin in terms of our universal Gaussian basis set is as accurate as that provided by the numerical finite difference method. The DF SCF energies calculated by Desclaux [At. Data. Nucl. Data Tables 12, 311 (1973)] (apart from a typographic error for Fr pointed out here) are higher than those reported here for atoms of some of the superheavy transactinide elements by as much as 5 hartrees (136 eV). We believe that this is due to the use by Desclaux of much larger atomic masses than the currently accepted values for these elements.

Replica exchange simulation of reversible folding/unfolding of the Trp-cage miniprotein in explicit solvent: on the structure and possible role of internal water.

PubMed

Paschek, Dietmar; Nymeyer, Hugh; García, Angel E

2007-03-01

We simulate the folding/unfolding equilibrium of the 20-residue miniprotein Trp-cage. We use replica exchange molecular dynamics simulations of the AMBER94 atomic detail model of the protein explicitly solvated by water, starting from a completely unfolded configuration. We employ a total of 40 replicas, covering the temperature range between 280 and 538 K. Individual simulation lengths of 100 ns sum up to a total simulation time of about 4 micros. Without any bias, we observe the folding of the protein into the native state with an unfolding-transition temperature of about 440 K. The native state is characterized by a distribution of root mean square distances (RMSD) from the NMR data that peaks at 1.8A, and is as low as 0.4A. We show that equilibration times of about 40 ns are required to yield convergence. A folded configuration in the entire extended ensemble is found to have a lifetime of about 31 ns. In a clamp-like motion, the Trp-cage opens up during thermal denaturation. In line with fluorescence quenching experiments, the Trp-residue sidechain gets hydrated when the protein opens up, roughly doubling the number of water molecules in the first solvation shell. We find the helical propensity of the helical domain of Trp-cage rather well preserved even at very high temperatures. In the folded state, we can identify states with one and two buried internal water molecules interconnecting parts of the Trp-cage molecule by hydrogen bonds. The loss of hydrogen bonds of these buried water molecules in the folded state with increasing temperature is likely to destabilize the folded state at elevated temperatures.

Synthesis of fullerene@gold core-shell nanostructures.

PubMed

Ren, Yupeng; Paira, Priyankar; Nayak, Tapas Ranjan; Ang, Wee Han; Pastorin, Giorgia

2011-07-21

A "direct encapsulation" method was developed for the synthesis of highly stable water-soluble fullerene@gold core-shell nanostructures, with gold nanoshells showing either closed or porous morphology. This gold nano-shell coating formed a "nano-oven", capable of decomposing encapsulated fullerene molecules rapidly when irradiated by laser. We envisaged this being a useful tool for chemical reactions as well as a novel scaffold for nano-material synthesis.

Synthesis of Polylactide-Based Core-Shell Interface Cross-Linked Micelles for Anticancer Drug Delivery.

PubMed

Chen, Chih-Kuang; Lin, Wei-Jen; Hsia, Yu; Lo, Leu-Wei

2017-03-01

Well-defined poly(ethylene glycol)-b-allyl functional polylactide-b-polylactides (PEG-APLA-PLAs) are synthesized through sequential ring-opening polymerization. PEG-APLA-PLAs that have amphiphilic properties and reactive allyl side chains on their intermediate blocks are successfully transferred to core-shell interface cross-linked micelles (ICMs) by micellization and UV-initiated irradiation. ICMs have demonstrated enhanced colloidal stability in physiological-mimicking media. Hydrophobic molecules such as Nile Red or doxorubicin (Dox) are readily loaded into ICMs; the resulting drug-ICM formulations possess slow and sustained drug release profiles under physiological-mimicking conditions. ICMs exhibit negligible cytotoxicity in human uterine sarcoma cancer cells by using biodegradable aliphatic polyester as the hydrophobic segments. Relative to free Dox, Dox-loaded ICMs show a reduced cytotoxicity due to the late intracellular release of Dox from ICMs. Overall, ICMs represent a new type of biodegradable cross-linked micelle and can be employed as a promising platform for delivering a broad variety of hydrophobic drugs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic study of the benchmark Mn+-H2 complex.

PubMed

Dryza, Viktoras; Poad, Berwyck L J; Bieske, Evan J

2009-05-28

We have recorded the rotationally resolved infrared spectrum of the weakly bound Mn+-H2 complex in the H-H stretch region (4022-4078 cm(-1)) by monitoring Mn+ photodissociation products. The band center of Mn+-H2, the H-H stretch transition, is shifted by -111.8 cm(-1) from the transition of the free H2 molecule. The spectroscopic data suggest that the Mn+-H2 complex consists of a slightly perturbed H2 molecule attached to the Mn+ ion in a T-shaped configuration with a vibrationally averaged intermolecular separation of 2.73 A. Together with the measured Mn+...H2 binding energy of 7.9 kJ/mol (Weis, P.; et al. J. Phys. Chem. A 1997, 101, 2809.), the spectroscopic parameters establish Mn+-H2 as the most thoroughly characterized transition-metal cation-dihydrogen complex and a benchmark for calibrating quantum chemical calculations on noncovalent systems involving open d-shell configurations. Such systems are of possible importance for hydrogen storage applications.

Facile synthesis of terminal-alkyne bioorthogonal molecules for live -cell surface-enhanced Raman scattering imaging through Au-core and silver/dopamine-shell nanotags.

PubMed

Chen, Meng; Zhang, Ling; Yang, Bo; Gao, Mingxia; Zhang, Xiangmin

2018-03-01

Alkyne is unique, specific and biocompatible in the Raman-silent region of the cell, but there still remains a challenge to achieve ultrasensitive detection in living systems due to its weak Raman scattering. Herein, a terminal alkyne ((E)-2-[4-(ethynylbenzylidene)amino]ethane-1-thiol (EBAE)) with surface-enhanced Raman scattering is synthesized. The EBAE molecule possesses S- and C-termini, which can be directly bonded to gold nanoparticles and dopamine/silver by forming the Au-S chemical bond and the carbon-metal bond, respectively. The distance between Raman reporter and AuNPs/AgNPs can be reduced, contributing to forming hot-spot-based SERS substrate. The alkyne functionalized nanoparticles are based on Au core and encapsulating polydopamine shell, defined as Au-core and dopamine/Ag-shell (ACDS). The bimetallic ACDS induce strong SERS signals for molecular imaging that arise from the strong electromagnetic field. Furthermore, the EBAE provides a distinct peak in the cellular Raman-silent region with nearly zero background interference. The EBAE Raman signals could be tremendously enhanced when the Raman reporter is located at the middle of the Au-core and dopamine/Ag-shell. Therefore, this work could have huge potential benefits for the highly sensitive detection of intercellular information delivery by connecting the recognition molecules in biomedical diagnostics. Graphical abstract Terminal-alkyne-functionalized Au-core and silver/dopamine-shell nanotags for live-cell surface-enhanced Raman scattering imaging.

Monodisperse Magneto-Fluorescent Bifunctional Nanoprobes for Bioapplications

NASA Astrophysics Data System (ADS)

Zhang, Hongwang; Huang, Heng; Pralle, Arnd; Zeng, Hao

2013-03-01

We present the work on the synthesis of dye-doped monodisperse Fe/SiO2 core/shell nanoparticles as bifunctional probes for bioapplications. Magnetic nanoparticles (NP) have been widely studied as nano-probes for bio-imaging, sensing as well as for cancer therapy. Among all the NPs, Fe NPs have been the focus because they have very high magnetization. However, Fe NPs are usually not stable in ambient due to the fast surface oxidation of the NPs. On the other hand, dye molecules have long been used as probes for bio-imaging. But they are sensitive to environmental conditions. It requires passivation for both so that they can be stable for applications. In this work, monodisperse Fe NPs with sizes ranging from 13-20 nm have been synthesized through the chemical thermal-decomposition in a solution. Silica shells were then coated on the Fe NPs by a two-phase oil-in-water method. Dye molecules were first bonded to a silica precursor and then encapsulated into the silica shell during the coating process. The silica shells protect both the Fe NPs and dye molecules, which makes them as robust probes. The dye doped Fe/SiO2 core/shell NPs remain both highly magnetic and highly fluorescent. The stable dye doped Fe/SiO2NPs have been used as a dual functional probe for both magnetic heating and local nanoscale temperature sending, and their performance will be reported. Research supported by NSF DMR 0547036, DMR1104994.

Computational modeling of the effective Young's modulus values of fullerene molecules: a combined molecular dynamics simulation and continuum shell model.

PubMed

Ghavanloo, Esmaeal; Izadi, Razie; Nayebi, Ali

2018-02-28

Estimating the Young's modulus of a structure in the nanometer size range is a difficult task. The reliable determination of this parameter is, however, important in both basic and applied research. In this study, by combining molecular dynamics (MD) simulations and continuum shell theory, we designed a new approach to determining the Young's modulus values of different spherical fullerenes. The results indicate that the Young's modulus values of fullerene molecules decrease nonlinearly with increasing molecule size and understandably tend to the Young's modulus of an ideal flat graphene sheet at large molecular radii. To the best of our knowledge, this is first time that a combined atomistic-continuum method which can predict the Young's modulus values of fullerene molecules with high precision has been reported.

Multiconfigurational short-range density-functional theory for open-shell systems

NASA Astrophysics Data System (ADS)

Hedegârd, Erik Donovan; Toulouse, Julien; Jensen, Hans Jørgen Aagaard

2018-06-01

Many chemical systems cannot be described by quantum chemistry methods based on a single-reference wave function. Accurate predictions of energetic and spectroscopic properties require a delicate balance between describing the most important configurations (static correlation) and obtaining dynamical correlation efficiently. The former is most naturally done through a multiconfigurational (MC) wave function, whereas the latter can be done by, e.g., perturbation theory. We have employed a different strategy, namely, a hybrid between multiconfigurational wave functions and density-functional theory (DFT) based on range separation. The method is denoted by MC short-range DFT (MC-srDFT) and is more efficient than perturbative approaches as it capitalizes on the efficient treatment of the (short-range) dynamical correlation by DFT approximations. In turn, the method also improves DFT with standard approximations through the ability of multiconfigurational wave functions to recover large parts of the static correlation. Until now, our implementation was restricted to closed-shell systems, and to lift this restriction, we present here the generalization of MC-srDFT to open-shell cases. The additional terms required to treat open-shell systems are derived and implemented in the DALTON program. This new method for open-shell systems is illustrated on dioxygen and [Fe(H2O)6]3+.

Size-tunable drug-delivery capsules composed of a magnetic nanoshell.

PubMed

Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa

2012-01-01

Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems.

Size-tunable drug-delivery capsules composed of a magnetic nanoshell

PubMed Central

Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa

2012-01-01

Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems. PMID:23507895

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

Eriksen, Janus J., E-mail: janusje@chem.au.dk; Jørgensen, Poul; Matthews, Devin A.

The accuracy at which total energies of open-shell atoms and organic radicals may be calculated is assessed for selected coupled cluster perturbative triples expansions, all of which augment the coupled cluster singles and doubles (CCSD) energy by a non-iterative correction for the effect of triple excitations. Namely, the second- through sixth-order models of the recently proposed CCSD(T–n) triples series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)] are compared to the acclaimed CCSD(T) model for both unrestricted as well as restricted open-shell Hartree-Fock (UHF/ROHF) reference determinants. By comparing UHF- and ROHF-based statistical results for a test setmore » of 18 modest-sized open-shell species with comparable RHF-based results, no behavioral differences are observed for the higher-order models of the CCSD(T–n) series in their correlated descriptions of closed- and open-shell species. In particular, we find that the convergence rate throughout the series towards the coupled cluster singles, doubles, and triples (CCSDT) solution is identical for the two cases. For the CCSD(T) model, on the other hand, not only its numerical consistency, but also its established, yet fortuitous cancellation of errors breaks down in the transition from closed- to open-shell systems. The higher-order CCSD(T–n) models (orders n > 3) thus offer a consistent and significant improvement in accuracy relative to CCSDT over the CCSD(T) model, equally for RHF, UHF, and ROHF reference determinants, albeit at an increased computational cost.« less

Lifetime of inner-shell hole states of Ar (2p) and Kr (3d) using equation-of-motion coupled cluster method

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

Ghosh, Aryya; Vaval, Nayana, E-mail: np.vaval@ncl.res.in; Pal, Sourav

2015-07-14

Auger decay is an efficient ultrafast relaxation process of core-shell or inner-shell excited atom or molecule. Generally, it occurs in femto-second or even atto-second time domain. Direct measurement of lifetimes of Auger process of single ionized and double ionized inner-shell state of an atom or molecule is an extremely difficult task. In this paper, we have applied the highly correlated complex absorbing potential-equation-of-motion coupled cluster (CAP-EOMCC) approach which is a combination of CAP and EOMCC approach to calculate the lifetime of the states arising from 2p inner-shell ionization of an Ar atom and 3d inner-shell ionization of Kr atom. Wemore » have also calculated the lifetime of Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}D, Ar{sup 2+}(2p{sup −1}3p{sup −1}) {sup 1}S, and Ar{sup 2+}(2p{sup −1}3s{sup −1}) {sup 1}P double ionized states. The predicted results are compared with the other theoretical results as well as experimental results available in the literature.« less

High ink absorption performance of inkjet printing based on SiO2@Al13 core-shell composites

NASA Astrophysics Data System (ADS)

Chen, YiFan; Jiang, Bo; Liu, Li; Du, Yunzhe; Zhang, Tong; Zhao, LiWei; Huang, YuDong

2018-04-01

The increasing growth of the inkjet market makes the inkjet printing more necessary. A composite material based on core-shell structure has been developed and applied to prepare inkjet printing layer. In this contribution, the ink printing record layers based on SiO2@Al13 core-shell composite was elaborated. The prepared core-shell composite materials were characterized by X-ray photoelectron spectroscopy (XPS), zeta potential, X-ray diffraction (XRD), scanning electron microscopy (SEM). The results proved the presence of electrostatic adsorption between SiO2 molecules and Al13 molecules with the formation of the well-dispersed system. In addition, based on the adsorption and the liquid permeability analysis, SiO2@Al13 ink printing record layer achieved a relatively high ink uptake (2.5 gmm-1) and permeability (87%), respectively. The smoothness and glossiness of SiO2@Al13 record layers were higher than SiO2 record layers. The core-shell structure facilitated the dispersion of the silica, thereby improved its ink absorption performance and made the clear printed image. Thus, the proposed procedure based on SiO2@Al13 core-shell structure of dye particles could be applied as a promising strategy for inkjet printing.

A code for analysis of the fine structure in near-rigid weakly-bonded open-shell complexes that consist of a diatomic radical in a Σ3 state and a closed-shell molecule

NASA Astrophysics Data System (ADS)

Fawzy, Wafaa M.

2010-10-01

A FORTRAN code is developed for simulation and fitting the fine structure of a planar weakly-bonded open-shell complex that consists of a diatomic radical in a Σ3 electronic state and a diatomic or a polyatomic closed-shell molecule. The program sets up the proper total Hamiltonian matrix for a given J value and takes account of electron-spin-electron-spin, electron-spin rotation interactions, and the quartic and sextic centrifugal distortion terms within the complex. Also, R-dependence of electron-spin-electron-spin and electron-spin rotation couplings are considered. The code does not take account of effects of large-amplitude internal rotation of the diatomic radical within the complex. It is assumed that the complex has a well defined equilibrium geometry so that effects of large amplitude motion are negligible. Therefore, the computer code is suitable for a near-rigid rotor. Numerical diagonalization of the matrix provides the eigenvalues and the eigenfunctions that are necessary for calculating energy levels, frequencies, relative intensities of infrared or microwave transitions, and expectation values of the quantum numbers within the complex. Goodness of all the quantum numbers, with exception of J and parity, depends on relative sizes of the product of the rotational constants and quantum numbers (i.e. BJ, CJ, and AK), electron-spin-electron-spin, and electron-spin rotation couplings, as well as the geometry of the complex. Therefore, expectation values of the quantum numbers are calculated in the eigenfunctions basis of the complex. The computational time for the least squares fits has been significantly reduced by using the Hellman-Feynman theory for calculating the derivatives. The computer code is useful for analysis of high resolution infrared and microwave spectra of a planar near-rigid weakly-bonded open-shell complex that contains a diatomic fragment in a Σ3 electronic state and a closed-shell molecule. The computer program was successfully applied to analysis and fitting the observed high resolution infrared spectra of the O 2sbnd HF/O 2sbnd DF and O 2sbnd N 2O complexes. Test input file for simulation and fitting the high resolution infrared spectrum of the O 2sbnd DF complex is provided. Program summaryProgram title: TSIG_COMP Catalogue identifier: AEGM_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEGM_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 10 030 No. of bytes in distributed program, including test data, etc.: 51 663 Distribution format: tar.gz Programming language: Fortran 90, free format Computer: SGI Origin 3400, workstations and PCs Operating system: Linux, UNIX and Windows (see Restrictions below) RAM: Case dependent Classification: 16.2 Nature of problem: TSIG_COMP calculates frequencies, relative intensities, and expectation values of the various quantum numbers and parities of bound states involved in allowed ro-vibrational transitions in semi-rigid planar weakly-bonded open-shell complexes. The complexes of interest contain a free radical in a Σ3 state and a closed-shell partner, where the electron-spin-electron-spin interaction, electron-spin rotation interaction, and centrifugal forces significantly modify the spectral patterns. To date, ab initio methods are incapable of taking these effects into account to provide accurate predictions for the ro-vibrational energy levels of the complexes of interest. In the TSIG_COMP program, the problem is solved by using the proper effective Hamiltonian and molecular basis set. Solution method: The program uses a Hamiltonian operator that takes into account vibration, end-over-end rotation, electron-spin-electron-spin and electron-spin rotation interactions as well as the various centrifugal distortion terms. The Hamiltonian operator and the molecular basis set are used to set up the Hamiltonian matrix in the inertial axis system of the complex of interest. Diagonalization of the Hamiltonian matrix provides the eigenvalues and the eigenfunctions for the bound ro-vibrational states. These eigenvalues and eigenfunctions are used to calculate frequencies and relative intensities of the allowed infrared or microwave transitions as well as expectation values of all the quantum numbers and parities of states involved in the transitions. The program employs the method of least squares fits to fit the observed frequencies to the calculated frequencies to provide the molecular parameters that determine the geometry of the complex of interest. Restrictions: The number of transitions and parameters included in the fits is limited to 80 parameters and 200 transitions. However, these numbers can be increased by adjusting dimensions of the arrays (not recommended). Running the program under MS windows is recommended for simulations of any number of transitions and for fitting a relatively small number of parameters and transitions (maximum 15 parameters and 82 transitions), for fitting larger number of parameters run time error may occur. Because spectra of weakly bonded complexes are recorded at low temperatures, in most of cases fittings can be performed under MS windows. Running time: Problem-dependent. The provided test input for Linux fits 82 transitions and 21 parameters, the actual run time is 62 minutes. The provided test input file for MS windows fits 82 transitions and 15 parameters; the actual runtime is 5 minutes.

Silica diatom shells tailored with Au nanoparticles enable sensitive analysis of molecules for biological, safety and environment applications.

PubMed

Onesto, V; Villani, M; Coluccio, M L; Majewska, R; Alabastri, A; Battista, E; Schirato, A; Calestani, D; Coppedé, N; Cesarelli, M; Amato, F; Di Fabrizio, E; Gentile, F

2018-04-10

Diatom shells are a natural, theoretically unlimited material composed of silicon dioxide, with regular patterns of pores penetrating through their surface. For their characteristics, diatom shells show promise to be used as low cost, highly efficient drug carriers, sensor devices or other micro-devices. Here, we demonstrate diatom shells functionalized with gold nanoparticles for the harvesting and detection of biological analytes (bovine serum albumin-BSA) and chemical pollutants (mineral oil) in low abundance ranges, for applications in bioengineering, medicine, safety, and pollution monitoring.

Microsolvation of the potassium ion with aromatic rings: comparison between hexafluorobenzene and benzene.

PubMed

Marques, J M C; Llanio-Trujillo, J L; Albertí, M; Aguilar, A; Pirani, F

2013-08-22

We employ a recently developed methodology to study structural and energetic properties of the first solvation shells of the potassium ion in nonpolar environments due to aromatic rings, which is important to understand the selectivity of several biochemical phenomena. Our evolutionary algorithm is used in the global optimization study of clusters formed of K(+) solvated with hexafluorobenzene (HFBz) molecules. The global intermolecular interaction for these clusters has been decomposed in HFBz-HFBz and in K(+)-HFBz contributions, using a potential model based on different decompositions of the molecular polarizability of hexafluorobenzene. Putative global minimum structures of microsolvation clusters up to 21 hexafluorobenzene molecules were obtained and compared with the analogous K(+)-benzene clusters reported in our previous work (J. Phys. Chem. A 2012, 116, 4947-4956). We have found that both K(+)-(Bz)n and K(+)-(HFBz)n clusters show a strong magic number around the closure of the first solvation shell. Nonetheless, all K(+)-benzene clusters have essentially the same first solvation shell geometry with four solvent molecules around the ion, whereas the corresponding one for K(+)-(HFBz)n is completed with nine HFBz species, and its structural motif varies as n increases. This is attributed to the ion-solvent interaction that has a larger magnitude for K(+)-Bz than in the case of K(+)-HFBz. In addition, the ability of having more HFBz than Bz molecules around K(+) in the first solvation shell is intimately related to the inversion in the sign of the quadrupole moment of the two solvent species, which leads to a distinct ion-solvent geometry of approach.

Spin density and orbital optimization in open shell systems: A rational and computationally efficient proposal

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

Giner, Emmanuel, E-mail: gnrmnl@unife.it; Angeli, Celestino, E-mail: anc@unife.it

2016-03-14

The present work describes a new method to compute accurate spin densities for open shell systems. The proposed approach follows two steps: first, it provides molecular orbitals which correctly take into account the spin delocalization; second, a proper CI treatment allows to account for the spin polarization effect while keeping a restricted formalism and avoiding spin contamination. The main idea of the optimization procedure is based on the orbital relaxation of the various charge transfer determinants responsible for the spin delocalization. The algorithm is tested and compared to other existing methods on a series of organic and inorganic open shellmore » systems. The results reported here show that the new approach (almost black-box) provides accurate spin densities at a reasonable computational cost making it suitable for a systematic study of open shell systems.« less

Dynamical discrete/continuum linear response shells theory of solvation: convergence test for NH4+ and OH- ions in water solution using DFT and DFTB methods.

PubMed

de Lima, Guilherme Ferreira; Duarte, Hélio Anderson; Pliego, Josefredo R

2010-12-09

A new dynamical discrete/continuum solvation model was tested for NH(4)(+) and OH(-) ions in water solvent. The method is similar to continuum solvation models in a sense that the linear response approximation is used. However, different from pure continuum models, explicit solvent molecules are included in the inner shell, which allows adequate treatment of specific solute-solvent interactions present in the first solvation shell, the main drawback of continuum models. Molecular dynamics calculations coupled with SCC-DFTB method are used to generate the configurations of the solute in a box with 64 water molecules, while the interaction energies are calculated at the DFT level. We have tested the convergence of the method using a variable number of explicit water molecules and it was found that even a small number of waters (as low as 14) are able to produce converged values. Our results also point out that the Born model, often used for long-range correction, is not reliable and our method should be applied for more accurate calculations.

Bottom head to shell junction assembly for a boiling water nuclear reactor

DOEpatents

Fife, Alex Blair; Ballas, Gary J.

1998-01-01

A bottom head to shell junction assembly which, in one embodiment, includes an annular forging having an integrally formed pump deck and shroud support is described. In the one embodiment, the annular forging also includes a top, cylindrical shaped end configured to be welded to one end of the pressure vessel cylindrical shell and a bottom, conical shaped end configured to be welded to the disk shaped bottom head. Reactor internal pump nozzles also are integrally formed in the annular forging. The nozzles do not include any internal or external projections. Stubs are formed in each nozzle opening to facilitate welding a pump housing to the forging. Also, an upper portion of each nozzle opening is configured to receive a portion of a diffuser coupled to a pump shaft which extends through the nozzle opening. Diffuser openings are formed in the integral pump deck to provide additional support for the pump impellers. The diffuser opening is sized so that a pump impeller can extend at least partially therethrough. The pump impeller is connected to the pump shaft which extends through the nozzle opening.

Bottom head to shell junction assembly for a boiling water nuclear reactor

DOEpatents

Fife, A.B.; Ballas, G.J.

1998-02-24

A bottom head to shell junction assembly which, in one embodiment, includes an annular forging having an integrally formed pump deck and shroud support is described. In the one embodiment, the annular forging also includes a top, cylindrical shaped end configured to be welded to one end of the pressure vessel cylindrical shell and a bottom, conical shaped end configured to be welded to the disk shaped bottom head. Reactor internal pump nozzles also are integrally formed in the annular forging. The nozzles do not include any internal or external projections. Stubs are formed in each nozzle opening to facilitate welding a pump housing to the forging. Also, an upper portion of each nozzle opening is configured to receive a portion of a diffuser coupled to a pump shaft which extends through the nozzle opening. Diffuser openings are formed in the integral pump deck to provide additional support for the pump impellers. The diffuser opening is sized so that a pump impeller can extend at least partially therethrough. The pump impeller is connected to the pump shaft which extends through the nozzle opening. 5 figs.

Chemical complexity in the winds of the oxygen-rich supergiant star VY Canis Majoris

NASA Astrophysics Data System (ADS)

Ziurys, L. M.; Milam, S. N.; Apponi, A. J.; Woolf, N. J.

2007-06-01

The interstellar medium is enriched primarily by matter ejected from old, evolved stars. The outflows from these stars create spherical envelopes, which foster gas-phase chemistry. The chemical complexity in circumstellar shells was originally thought to be dominated by the elemental carbon to oxygen ratio. Observations have suggested that envelopes with more carbon than oxygen have a significantly greater abundance of molecules than their oxygen-rich analogues. Here we report observations of molecules in the oxygen-rich shell of the red supergiant star VY Canis Majoris (VY CMa). A variety of unexpected chemical compounds have been identified, including NaCl, PN, HNC and HCO+. From the spectral line profiles, the molecules can be distinguished as arising from three distinct kinematic regions: a spherical outflow, a tightly collimated, blue-shifted expansion, and a directed, red-shifted flow. Certain species (SiO, PN and NaCl) exclusively trace the spherical flow, whereas HNC and sulphur-bearing molecules (amongst others) are selectively created in the two expansions, perhaps arising from shock waves. CO, HCN, CS and HCO+ exist in all three components. Despite the oxygen-rich environment, HCN seems to be as abundant as CO. These results suggest that oxygen-rich shells may be as chemically diverse as their carbon counterparts.

Chemical complexity in the winds of the oxygen-rich supergiant star VY Canis Majoris.

PubMed

Ziurys, L M; Milam, S N; Apponi, A J; Woolf, N J

2007-06-28

The interstellar medium is enriched primarily by matter ejected from old, evolved stars. The outflows from these stars create spherical envelopes, which foster gas-phase chemistry. The chemical complexity in circumstellar shells was originally thought to be dominated by the elemental carbon to oxygen ratio. Observations have suggested that envelopes with more carbon than oxygen have a significantly greater abundance of molecules than their oxygen-rich analogues. Here we report observations of molecules in the oxygen-rich shell of the red supergiant star VY Canis Majoris (VY CMa). A variety of unexpected chemical compounds have been identified, including NaCl, PN, HNC and HCO+. From the spectral line profiles, the molecules can be distinguished as arising from three distinct kinematic regions: a spherical outflow, a tightly collimated, blue-shifted expansion, and a directed, red-shifted flow. Certain species (SiO, PN and NaCl) exclusively trace the spherical flow, whereas HNC and sulphur-bearing molecules (amongst others) are selectively created in the two expansions, perhaps arising from shock waves. CO, HCN, CS and HCO+ exist in all three components. Despite the oxygen-rich environment, HCN seems to be as abundant as CO. These results suggest that oxygen-rich shells may be as chemically diverse as their carbon counterparts.

Dynamic model of open shell structures buried in poroelastic soils

NASA Astrophysics Data System (ADS)

Bordón, J. D. R.; Aznárez, J. J.; Maeso, O.

2017-08-01

This paper is concerned with a three-dimensional time harmonic model of open shell structures buried in poroelastic soils. It combines the dual boundary element method (DBEM) for treating the soil and shell finite elements for modelling the structure, leading to a simple and efficient representation of buried open shell structures. A new fully regularised hypersingular boundary integral equation (HBIE) has been developed to this aim, which is then used to build the pair of dual BIEs necessary to formulate the DBEM for Biot poroelasticity. The new regularised HBIE is validated against a problem with analytical solution. The model is used in a wave diffraction problem in order to show its effectiveness. It offers excellent agreement for length to thickness ratios greater than 10, and relatively coarse meshes. The model is also applied to the calculation of impedances of bucket foundations. It is found that all impedances except the torsional one depend considerably on hydraulic conductivity within the typical frequency range of interest of offshore wind turbines.

The environmental effect on the radial breathing mode of carbon nanotubes. II. Shell model approximation for internally and externally adsorbed fluids

NASA Astrophysics Data System (ADS)

Longhurst, M. J.; Quirke, N.

2006-11-01

We have previously shown that the upshift in the radial breathing mode (RBM) of closed (or infinite) carbon nanotubes in solution is almost entirely due to coupling of the RBM with an adsorbed layer of fluid on the nanotube surface. The upshift can be modeled analytically by considering the adsorbed fluid as an infinitesimally thin shell, which interacts with the nanotube via a continuum Lennard-Jones potential. Here we extend the model to include internally as well as externally adsorbed waterlike molecules, and find that filling the nanotubes leads to an additional upshift of two to six wave numbers. We show that using molecular dynamics, the RBM can be accurately reproduced by replacing the fluid molecules with a mean field harmonic shell potential, greatly reducing simulation times.

Inner shell radial pin geometry and mounting arrangement

DOEpatents

Leach, David; Bergendahl, Peter Allen

2002-01-01

Circumferentially spaced arrays of support pins are disposed through access openings in an outer turbine shell and have projections received in recesses in forward and aft sections of an inner turbine shell supported from the outer shell. The projections have arcuate sides in a circumferential direction affording line contacts with the side walls of the recesses and are spaced from end faces of the recesses, enabling radial and axial expansion and contraction of the inner shell relative to the outer shell. All loads are taken up in a tangential direction by the outer shell with the support pins taking no radial loadings.

Structure of the first- and second-neighbor shells of simulated water: Quantitative relation to translational and orientational order

NASA Astrophysics Data System (ADS)

Yan, Zhenyu; Buldyrev, Sergey V.; Kumar, Pradeep; Giovambattista, Nicolas; Debenedetti, Pablo G.; Stanley, H. Eugene

2007-11-01

We perform molecular dynamics simulations of water using the five-site transferable interaction potential (TIP5P) model to quantify structural order in both the first shell (defined by four nearest neighbors) and second shell (defined by twelve next-nearest neighbors) of a central water molecule. We find that the anomalous decrease of orientational order upon compression occurs in both shells, but the anomalous decrease of translational order upon compression occurs mainly in the second shell. The decreases of translational order and orientational order upon compression (called the “structural anomaly”) are thus correlated only in the second shell. Our findings quantitatively confirm the qualitative idea that the thermodynamic, structural, and hence dynamic anomalies of water are related to changes upon compression in the second shell.

Core-Shell-Corona Micelles with a Responsive Shell.

PubMed

Gohy, Jean-François; Willet, Nicolas; Varshney, Sunil; Zhang, Jian-Xin; Jérôme, Robert

2001-09-03

A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Exploiting the spatial locality of electron correlation within the parametric two-electron reduced-density-matrix method

NASA Astrophysics Data System (ADS)

DePrince, A. Eugene; Mazziotti, David A.

2010-01-01

The parametric variational two-electron reduced-density-matrix (2-RDM) method is applied to computing electronic correlation energies of medium-to-large molecular systems by exploiting the spatial locality of electron correlation within the framework of the cluster-in-molecule (CIM) approximation [S. Li et al., J. Comput. Chem. 23, 238 (2002); J. Chem. Phys. 125, 074109 (2006)]. The 2-RDMs of individual molecular fragments within a molecule are determined, and selected portions of these 2-RDMs are recombined to yield an accurate approximation to the correlation energy of the entire molecule. In addition to extending CIM to the parametric 2-RDM method, we (i) suggest a more systematic selection of atomic-orbital domains than that presented in previous CIM studies and (ii) generalize the CIM method for open-shell quantum systems. The resulting method is tested with a series of polyacetylene molecules, water clusters, and diazobenzene derivatives in minimal and nonminimal basis sets. Calculations show that the computational cost of the method scales linearly with system size. We also compute hydrogen-abstraction energies for a series of hydroxyurea derivatives. Abstraction of hydrogen from hydroxyurea is thought to be a key step in its treatment of sickle cell anemia; the design of hydroxyurea derivatives that oxidize more rapidly is one approach to devising more effective treatments.

Au-Ag-Au double shell nanoparticles-based localized surface plasmon resonance and surface-enhanced Raman scattering biosensor for sensitive detection of 2-mercapto-1-methylimidazole.

PubMed

Liao, Xue; Chen, Yanhua; Qin, Meihong; Chen, Yang; Yang, Lei; Zhang, Hanqi; Tian, Yuan

2013-12-15

In this paper, Au-Ag-Au double shell nanoparticles were prepared based on the reduction of the metal salts HAuCl4 and AgNO3 at the surface of seed particles. Due to the synergistic effect between Au and Ag, the hybrid nanoparticles are particularly stable and show excellent performances on the detection of 2-mercapto-1-methylimidazole (methimazole). The binding of target molecule at the surface of Au-Ag-Au double shell nanoparticles was demonstrated based on both localized surface plasmon resonance (LSPR) and surface-enhanced Raman scattering (SERS) spectra. The LSPR intensity is directly proportional to the methimazole concentration in the range of 0.10-3.00×10(-7) mol L(-1). The SERS spectrum can be applied in identification of methimazole molecule. The LSPR coupled with SERS based on the Au-Ag-Au double shell nanoparticles would be very attractive for the quantitative determination and qualitative analysis of the analytes in medicines. © 2013 Elsevier B.V. All rights reserved.

Folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell composite particles: synthesis and application in drug release.

PubMed

Yang, Dandan; Wei, Kaiwei; Liu, Qi; Yang, Yong; Guo, Xue; Rong, Hongren; Cheng, Mei-Ling; Wang, Guoxiu

2013-07-01

A drug delivery system was designed by deliberately combining the useful functions into one entity, which was composed of magnetic ZnFe2O4 hollow microsphere as the core, and mesoporous silica with folic acid molecules as the outer shell. Amine groups coated magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NH2) composite particles were first synthesized by a one-pot direct co-condensation method. Subsequently a novel kind of folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NHFA) composite particles were synthesized by conjugating folic acid as targeted molecule to MZHM-MSS-NH2. Ibuprofen, a well-known antiphlogistic drug, was used as a model drug to assess the loading and releasing behavior of the composite microspheres. The results show that the MZHM-MSS-NHFA system has the higher capacity of drug storage and good sustained drug-release property. Copyright © 2013 Elsevier B.V. All rights reserved.

Ethanol Gas Detection Using a Yolk-Shell (Core-Shell) α-Fe2O3 Nanospheres as Sensing Material.

PubMed

Wang, LiLi; Lou, Zheng; Deng, Jianan; Zhang, Rui; Zhang, Tong

2015-06-17

Three-dimensional (3D) nanostructures of α-Fe2O3 materials, including both hollow sphere-shaped and yolk-shell (core-shell)-shaped, have been successfully synthesized via an environmentally friendly hydrothermal approach. By expertly adjusting the reaction time, the solid, hollow, and yolk-shell shaped α-Fe2O3 can be selectively synthesized. Yolk-shell α-Fe2O3 nanospheres display outer diameters of 350 nm, and the interstitial hollow spaces layer is intimately sandwiched between the inner and outer shell of α-Fe2O3 nanostructures. The possible growth mechanism of the yolk-shell nanostructure is proposed. The results showed that the well-defined bilayer interface effectively enhanced the sensing performance of the α-Fe2O3 nanostructures (i.e., yolk-shell α-Fe2O3@α-Fe2O3), owing predominantly to the unique nanostructure, thus facilitated the transport rate and augmented the adsorption quantity of the target gas molecule under gas detection.

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

PubMed

Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

2016-02-15

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

Microcavity surface plasmon resonance bio-sensors

NASA Astrophysics Data System (ADS)

Mosavian, Nazanin

This work discusses a miniature surface plasmon biosensor which uses a dielectric sub- micron diameter core with gold spherical shell. The shell has a subwavelength nanoaperture believed to excite stationary plasmon resonances at the biosensor's surface. The sub-micron cavity enhances the measurement sensitivity of molecules binding to the sensor surface. We used visible-range optical spectroscopy to study the wavelength shift as bio-molecules absorbed-desorbed at the shell surface. We also used Scanning Electron Microscopy (SEM) and Focused Ion Beam (FIB) ablation to study the characteristics of microcavity surface plasmon resonance sensor (MSPRS) and the inner structure formed with metal deposition and its spectrum. We found that resonances at 580 nm and 670 nm responded to bound test agents and that Surface Plasmon Resonance (SPR) sensor intensity could be used to differentiate between D-glucose and L-glucose. The responsiveness of the system depended upon the mechanical integrity of the metallic surface coating.

Molecular mechanisms of decomposition of hydrated Na+Cl- ion pairs under planar nanopore conditions

NASA Astrophysics Data System (ADS)

Shevkunov, S. V.

2017-02-01

The decomposition of Na+Cl- ion pairs under the conditions of a nanoscopic planar pore with structureless walls in a material contact with water vapor at 298 K is simulated by Monte Carlo method. The transition from the state of a contact ion pair (CIP) to the state of solvent-separated ion pair (SSIP) is shown to occur as a result of an increase in the vapor pressure over a pore after exceeding the threshold number of molecules in a hydrate shell. It is found that the planar form of a molecular cluster under the conditions of a narrow pore does not level an abrupt structural transition and the formation of hydrogen bonds in the hydrate shell starts after three molecules are added. The hydrogen bond length under pore conditions is found to be resistant to variations in the hydrate shell size and coincides with that in water under normal conditions.

Compressibility of the protein-water interface

NASA Astrophysics Data System (ADS)

Persson, Filip; Halle, Bertil

2018-06-01

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (˜0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ˜45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Compressibility of the protein-water interface.

PubMed

Persson, Filip; Halle, Bertil

2018-06-07

The compressibility of a protein relates to its stability, flexibility, and hydrophobic interactions, but the measurement, interpretation, and computation of this important thermodynamic parameter present technical and conceptual challenges. Here, we present a theoretical analysis of protein compressibility and apply it to molecular dynamics simulations of four globular proteins. Using additively weighted Voronoi tessellation, we decompose the solution compressibility into contributions from the protein and its hydration shells. We find that positively cross-correlated protein-water volume fluctuations account for more than half of the protein compressibility that governs the protein's pressure response, while the self correlations correspond to small (∼0.7%) fluctuations of the protein volume. The self compressibility is nearly the same as for ice, whereas the total protein compressibility, including cross correlations, is ∼45% of the bulk-water value. Taking the inhomogeneous solvent density into account, we decompose the experimentally accessible protein partial compressibility into intrinsic, hydration, and molecular exchange contributions and show how they can be computed with good statistical accuracy despite the dominant bulk-water contribution. The exchange contribution describes how the protein solution responds to an applied pressure by redistributing water molecules from lower to higher density; it is negligibly small for native proteins, but potentially important for non-native states. Because the hydration shell is an open system, the conventional closed-system compressibility definitions yield a pseudo-compressibility. We define an intrinsic shell compressibility, unaffected by occupation number fluctuations, and show that it approaches the bulk-water value exponentially with a decay "length" of one shell, less than the bulk-water compressibility correlation length. In the first hydration shell, the intrinsic compressibility is 25%-30% lower than in bulk water, whereas its self part is 15%-20% lower. These large reductions are caused mainly by the proximity to the more rigid protein and are not a consequence of the perturbed water structure.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf])

NASA Astrophysics Data System (ADS)

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J.; Cisneros, G. Andrés

2018-01-01

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]).

PubMed

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés

2018-01-14

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17 O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO 4 ]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf] - anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Chemical and thermal stability of core-shelled magnetite nanoparticles and solid silica

NASA Astrophysics Data System (ADS)

Cendrowski, Krzysztof; Sikora, Pawel; Zielinska, Beata; Horszczaruk, Elzbieta; Mijowska, Ewa

2017-06-01

Pristine nanoparticles of magnetite were coated by solid silica shell forming core/shell structure. 20 nm thick silica coating significantly enhanced the chemical and thermal stability of the iron oxide. Chemical and thermal stability of this structure has been compared to the magnetite coated by mesoporous shell and pristine magnetite nanoparticles. It is assumed that six-membered silica rings in a solid silica shell limit the rate of oxygen diffusion during thermal treatment in air and prevent the access of HCl molecules to the core during chemical etching. Therefore, the core/shell structure with a solid shell requires a longer time to induce the oxidation of iron oxide to a higher oxidation state and, basically, even strong concentrated acid such as HCl is not able to dissolve it totally in one month. This leads to the desired performance of the material in potential applications such as catalysis and environmental protection.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling.

PubMed

Wang, Zhifan; Hu, Shu; Wang, Fan; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.

Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

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

Wang, Zhifan; Hu, Shu; Guo, Jingwei

2015-04-14

In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis setmore » without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.« less

Dynamic Stacking Pathway of Perylene Dimers in Aromatic and Nonaromatic Solvents.

PubMed

Hollfelder, Manuel; Gekle, Stephan

2015-08-13

Using molecular dynamics simulations, we elucidate in detail the dynamics of the π-π stacking process of a perylene bisimide (PBI) dimer solvated in toluene. Our calculations show that the transition from the open (unstacked) to the stacked configuration is hindered by a small free energy barrier of approximately 1kBT in toluene but not in the nonaromatic solvent hexane. A similar effect is observed tor two non-covalently linked monomers. The origin of this barrier is traced back to π-π interactions between perylene and the aromatic solvent which are very similar in nature to those between two PBI monomers. The stacking process proceeds in three phases via two well-defined transition states: (i) in the first phase, the two PBI molecules share part of their respective solvation shells forming the first transition state. Further approach needs to squeeze out the shared solvent layer, thus creating the energy barrier. (ii) After removal of the separating solvent, the two PBIs form a second transition state with one monomer located at a random position in the other's solvation shell. (iii) Finally, the two PBIs slide on top of each other into their final stacked position.

QM/MM investigation of the concentration effects on the second-order nonlinear optical responses of solutions

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

Hidalgo Cardenuto, Marcelo, E-mail: marcelo.hidalgo@unamur.be, E-mail: benoit.champagne@unamur.be; Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP; Champagne, Benoît, E-mail: marcelo.hidalgo@unamur.be, E-mail: benoit.champagne@unamur.be

2014-12-21

A multiscale approach combining quantum mechanics (QM) and molecular mechanics methods has been employed to investigate the effects of solute-solute interactions and therefore of concentration on the first hyperpolarizability of solutions of nitrobenzene in benzene. First, spatial distributions of solute and solvent molecules are generated using Monte Carlo simulations where the intermolecular interactions are described using the Lennard-Jones potentials and Coulomb terms. Then, a reduced number of statistically-uncorrelated configurations are sampled and submitted to time-dependent Hartree-Fock calculations of the first hyperpolarizability. When only one molecule is described quantum-mechanically and is embedded in the electrostatic polarization field of the solution describedmore » by point charges, β{sub HRS} and β{sub //} as well as the depolarization ratio increase in parallel with the concentration in nitrobenzene. This effect is attributed to the increase of the polarization field associated with the presence of polar nitrobenzene molecules in the surrounding. Then, the first solvation shell is considered explicitly in the QM calculation to address solute-solute interactions effects. When the number of nitrobenzenes in the first solvation shell increases, β{sub HRS} and β{sub //} normalized to the number of nitrobenzene molecules decrease and this decrease attains roughly 50% when there are 3 nitrobenzene molecules in the first solvation shell. These drastic reductions of the first hyperpolarizability result from (partial) centro-symmetric arrangements between the nitrobenzene molecules, as supported by the relationship between β and the angle between the nitrobenzene charge transfer axes. Moreover, these β decreases originate mostly from the reduction of the dipolar β component, whereas the octupolar one is rather constant as a function of the nitrobenzene concentration.« less

N(2)O in small para-hydrogen clusters: Structures and energetics.

PubMed

Zhu, Hua; Xie, Daiqian

2009-04-30

We present the minimum-energy structures and energetics of clusters of the linear N(2)O molecule with small numbers of para-hydrogen molecules with pairwise additive potentials. Interaction energies of (p-H(2))-N(2)O and (p-H(2))-(p-H(2)) complexes were calculated by averaging the corresponding full-dimensional potentials over the H(2) angular coordinates. The averaged (p-H(2))-N(2)O potential has three minima corresponding to the T-shaped and the linear (p-H(2))-ONN and (p-H(2))-NNO structures. Optimization of the minimum-energy structures was performed using a Genetic Algorithm. It was found that p-H(2) molecules fill three solvation rings around the N(2)O axis, each of them containing up to five p-H(2) molecules, followed by accumulation of two p-H(2) molecules at the oxygen and nitrogen ends. The first solvation shell is completed at N = 17. The calculated chemical potential oscillates with cluster size up to the completed first solvation shell. These results are consistent with the available experimental measurements. (c) 2009 Wiley Periodicals, Inc.

Density functional theory for open-shell singlet biradicals

NASA Astrophysics Data System (ADS)

Gräfenstein, Jürgen; Kraka, Elfi; Cremer, Dieter

1998-05-01

The description of open-shell singlet (OSS) σ- π biradicals by density functional theory (DFT) requires at least a two-configurational (TC) or, in general, a MC-DFT approach, which bears many unsolved problems. These can be avoided by reformulating the TC description in the spirit of restricted open shell theory for singlets (ROSS) and developing an exchange-correlation functional for ROSS-DFT. ROSS-DFT turns out to lead to reliable descriptions of geometry and vibrational frequencies for OSS biradicals. The relative energies of the OSS states obtained at the ROSS-B3LYP/6-311G(d,p) level are often better than the corresponding ROSS-MP2 results. However, in those cases where spin polarization in a conjugated π systems plays a role, DFT predicts the triplet state related to the OSS state 2-4 kcal/mol too stable.

Switchable Opening and Closing of a Liquid Marble via Ultrasonic Levitation.

PubMed

Zang, Duyang; Li, Jun; Chen, Zhen; Zhai, Zhicong; Geng, Xingguo; Binks, Bernard P

2015-10-27

Liquid marbles have promising applications in the field of microreactors, where the opening and closing of their surfaces plays a central role. We have levitated liquid water marbles using an acoustic levitator and, thereby, achieved the manipulation of the particle shell in a controlled manner. Upon increasing the sound intensity, the stable levitated liquid marble changes from a quasi-sphere to a flattened ellipsoid. Interestingly, a cavity on the particle shell can be produced on the polar areas, which can be completely healed when decreasing the sound intensity, allowing it to serve as a microreactor. The integral of the acoustic radiation pressure on the part of the particle surface protruding into air is responsible for particle migration from the center of the liquid marble to the edge. Our results demonstrate that the opening and closing of the liquid marble particle shell can be conveniently achieved via acoustic levitation, opening up a new possibility to manipulate liquid marbles coated with non-ferromagnetic particles.

Characterization of the interface interaction of cobalt on top of copper- and iron-phthalocyanine.

PubMed

Schmitt, Felix; Sauther, Jens; Lach, Stefan; Ziegler, Christiane

2011-05-01

The electronic structure of the interface between ferromagnetic cobalt and the organic semiconductors copper- (CuPc) and iron-phthalocyanine (FePc) was investigated by means of photoemission spectroscopy (UPS, IPES, and XPS). These metal-phthalocyanine (MePc) molecules have an open shell structure and are known to show promising properties for their use in organic spintronics. In spintronic devices, the interface between ferromagnetic electrode and the organic layer determines the spin injection properties and is hence important for the quality of, e.g., a possible spin-valve device. For this purpose, cobalt was deposited onto the MePcs, such as in devices with ferromagnetic top contacts. The reported investigations reveal a diffusion of cobalt into the organic layers and chemical reactions at the interface.

Molecular beam mass spectrometer development

NASA Technical Reports Server (NTRS)

Brock, F. J.; Hueser, J. E.

1976-01-01

An analytical model, based on the kinetics theory of a drifting Maxwellian gas is used to determine the nonequilibrium molecular density distribution within a hemispherical shell open aft with its axis parallel to its velocity. The concept of a molecular shield in terrestrial orbit above 200 km is also analyzed using the kinetic theory of a drifting Maxwellian gas. Data are presented for the components of the gas density within the shield due to the free stream atmosphere, outgassing from the shield and enclosed experiments, and atmospheric gas scattered off a shield orbiter system. A description is given of a FORTRAN program for computating the three dimensional transition flow regime past the space shuttle orbiter that employs the Monte Carlo simulation method to model real flow by some thousands of simulated molecules.

Fine-structure-resolution for Rovibrational Excitation of CN Due to H2

NASA Astrophysics Data System (ADS)

Byrd, Nat; Yang, Benhui H.; Stancil, Phillip C.

2018-06-01

Diatomic molecules can be readily excited in interstellar environments exposed to intense UV radiation, such as the inner rim of a protoplanetary disk. Non-thermal populations of excited rovibrational levels can result, for example, following decay from electronically excited states to the electronic ground state. Competition between radiative decay and collisional processes, mostly due to H2, determine the resulting rovibrational emission spectrum. For CN, and other open-shell molecules, the resulting spectrum will be complicated due to fine-structure splitting of the rotational levels. In some cases, fine-structure resolution has been previously computed for rotational transitions in atom- or diatom-diatom collisional processes. Here we present the first fine-structure resolution for vibrational deexcitation for CN colliding with H2. The collisional cross sections were computed using a 6D potential energy surface with a full close-coupling approach. Fine-structure resolution is obtained by adopting an angular momentum recoupling scheme to transform the scattering matrices to a recoupled basis. Here we present low-energy calculations for the v=1 to 0 transition.This work was supported by NASA Grant NNX16AF09G.

Does the 4f-shell contribute to bonding in tetravalent lanthanide halides?

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

Ji, Wen-Xin; School of Chemistry and Chemical Engineering, Ningxia University, 750015 Yinchuan; Xu, Wei

2014-12-28

Lanthanide tetrahalide molecules LnX{sub 4} (Ln = Ce, Pr, Tb; X = F, Cl, Br, I) have been investigated by density functional theory at the levels of the relativistic Zero Order Regular Approximation and the relativistic energy-consistent pseudopotentials, using frozen small- and medium-cores. The calculated bond lengths and vibrational frequencies are close to the experimental data. Our calculations indicate 4f shell contributions to bonding in LnX{sub 4}, in particular for the early lanthanides, which show significant overlap between the Ln 4f-shell and the halogen np-shells. The 4f shells contribute to Ln-X bonding in LnX{sub 4} about one third more thanmore » in LnX{sub 3}.« less

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles.

PubMed

Ren, Ting; Erker, Wolfgang; Basché, Thomas; Schärtl, Wolfgang

2010-12-07

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.

A Facile Strategy for In Situ Core-Template-Functionalizing Siliceous Hollow Nanospheres for Guest Species Entrapment

PubMed Central

2009-01-01

The shell wall-functionalized siliceous hollow nanospheres (SHNs) with functional molecules represent an important class of nanocarriers for a rich range of potential applications. Herein, a self-templated approach has been developed for the synthesis of in situ functionalized SHNs, in which the biocompatible long-chain polycarboxylates (i.e., polyacrylate, polyaspartate, gelatin) provide the framework for silica precursor deposition by simply controlling chain conformation with divalent metal ions (i.e., Ca2+, Sr2+), without the intervention of any external templates. Metal ions play crucial roles in the formation of organic vesicle templates by modulating the long chains of polymers and preventing them from separation by washing process. We also show that, by in situ functionalizing the shell wall of SHNs, it is capable of entrapping nearly an eightfold quantity of vitamin Bc in comparison to the bare bulk silica nanospheres. These results confirm the feasibility of guest species entrapment in the functionalized shell wall, and SHNs are effective carriers of guest (bio-)molecules potentially for a variety of biomedical applications. By rationally choosing the functional (self-templating) molecules, this concept may represent a general strategy for the production of functionalized silica hollow structures. PMID:20596316

Solvation of carbonaceous molecules by para-H{sub 2} and ortho-D{sub 2} clusters. I. Polycyclic aromatic hydrocarbons

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

Calvo, F., E-mail: florent.calvo@univ-grenoble-alpes.fr; Yurtsever, E.

This work theoretically examines the progressive coating of planar polycyclic aromatic hydrocarbon (PAH) molecules ranging from benzene to circumcoronene (C{sub 54}H{sub 18}) by para-hydrogen and ortho-deuterium. The coarse-grained Silvera-Goldman potential has been extended to model the interactions between hydrogen molecules and individual atoms of the PAH and parametrized against quantum chemical calculations for benzene-H{sub 2}. Path-integral molecular dynamics simulations at 2 K were performed for increasingly large amounts of hydrogen coating the PAH up to the first solvation shell and beyond. From the simulations, various properties were determined such as the size of the first shell and its thickness asmore » well as the solvation energy. The degree of delocalization was notably quantified from an energy landscape perspective, by monitoring the fluctuations among inherent structures sampled by the trajectories. Our results generally demonstrate a high degree of localization owing to relatively strong interactions between hydrogen and the PAH, and qualitatively minor isotopic effects. In the limit of large hydrogen amounts, the shell size and solvation energy both follow approximate linear relations with the numbers of carbon and hydrogen in the PAH.« less

Solvation of carbonaceous molecules by para-H2 and ortho-D2 clusters. I. Polycyclic aromatic hydrocarbons.

PubMed

Calvo, F; Yurtsever, E

2016-06-14

This work theoretically examines the progressive coating of planar polycyclic aromatic hydrocarbon (PAH) molecules ranging from benzene to circumcoronene (C54H18) by para-hydrogen and ortho-deuterium. The coarse-grained Silvera-Goldman potential has been extended to model the interactions between hydrogen molecules and individual atoms of the PAH and parametrized against quantum chemical calculations for benzene-H2. Path-integral molecular dynamics simulations at 2 K were performed for increasingly large amounts of hydrogen coating the PAH up to the first solvation shell and beyond. From the simulations, various properties were determined such as the size of the first shell and its thickness as well as the solvation energy. The degree of delocalization was notably quantified from an energy landscape perspective, by monitoring the fluctuations among inherent structures sampled by the trajectories. Our results generally demonstrate a high degree of localization owing to relatively strong interactions between hydrogen and the PAH, and qualitatively minor isotopic effects. In the limit of large hydrogen amounts, the shell size and solvation energy both follow approximate linear relations with the numbers of carbon and hydrogen in the PAH.

Detection of MgCn in IRC + 10216: A new metal-bearing free radical

NASA Technical Reports Server (NTRS)

Ziurys, L. M.; Apponi, A. J.; Guelin, M.; Cernicharo, J.

1995-01-01

A new metal-containing molecule, MgCN, has been detected toward the late-type star IRC + 10216, using the NRAO 12 m and IRAM 30 m telescopes. The N = 11 approaches 10, 10 approaches 9, and 9 approaches 8 transtions of this species which has a (sup 2)Sigma(sup +) ground state, have been observed in the outer envelope of this object at 3 mm. For the N = 11 approaches 10 transitions, the two spin-rotation components are clearly resolved and conclusively identify this new radical. These measurements imply a column of density for MgCN of N(sub tot) approximately 10(exp 12)/sq cm in the outer shell, which corresponds to a fractional abundance of f approximately 7x10(exp -10). This molecule, the metastable isomer of MgNC, is the third metal-bearing species thus far identified in the outer shell of IRC + 10216, and its detection implies a ratio of MgNC/MgCN approximately 22/1. MgCN may be formed through a reaction scheme involving magnesium and HNC or CN, both prominent outer shell molecules, or through synthesis on grains.

Core-shell microspheres with porous nanostructured shells for liquid chromatography.

PubMed

Ahmed, Adham; Skinley, Kevin; Herodotou, Stephanie; Zhang, Haifei

2018-01-01

The development of new stationary phases has been the key aspect for fast and efficient high-performance liquid chromatography separation with relatively low backpressure. Core-shell particles, with a solid core and porous shell, have been extensively investigated and commercially manufactured in the last decade. The excellent performance of core-shell particles columns has been recorded for a wide range of analytes, covering small and large molecules, neutral and ionic (acidic and basic), biomolecules and metabolites. In this review, we first introduce the advance and advantages of core-shell particles (or more widely known as superficially porous particles) against non-porous particles and fully porous particles. This is followed by the detailed description of various methods used to fabricate core-shell particles. We then discuss the applications of common silica core-shell particles (mostly commercially manufactured), spheres-on-sphere particles and core-shell particles with a non-silica shell. This review concludes with a summary and perspective on the development of stationary phase materials for high-performance liquid chromatography applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition Formulas of Inorganic Compounds in Terms of Cluster Plus Glue Atom Model.

PubMed

Ma, Yanping; Dong, Dandan; Wu, Aimin; Dong, Chuang

2018-01-16

The present paper attempts to identify the molecule-like structural units in inorganic compounds, by applying the so-called "cluster plus glue atom model". This model, originating from metallic glasses and quasi-crystals, describes any structure in terms of a nearest-neighbor cluster and a few outer-shell glue atoms, expressed in the cluster formula [cluster](glue atoms). Similar to the case for normal molecules where the charge transfer occurs within the molecule to meet the commonly known octet electron rule, the octet state is reached after matching the nearest-neighbor cluster with certain outer-shell glue atoms. These kinds of structural units contain information on local atomic configuration, chemical composition, and electron numbers, just as for normal molecules. It is shown that the formulas of typical inorganic compounds, such as fluorides, oxides, and nitrides, satisfy a similar octet electron rule, with the total number of valence electrons per unit formula being multiples of eight.

Molecular Electronic Terms and Molecular Orbital Configurations.

ERIC Educational Resources Information Center

Mazo, R. M.

1990-01-01

Discussed are the molecular electronic terms which can arise from a given electronic configuration. Considered are simple cases, molecular states, direct products, closed shells, and open shells. Two examples are provided. (CW)

Förster resonance energy transfer mediated enhancement of the fluorescence lifetime of organic fluorophores to the millisecond range by coupling to Mn-doped CdS/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Kaiser, Uwe; Sabir, Nadeem; Carrillo-Carrion, Carolina; del Pino, Pablo; Bossi, Mariano; Heimbrodt, Wolfram; Parak, Wolfgang J.

2016-02-01

Manganese-doped CdS/ZnS quantum dots have been used as energy donors in a Förster-like resonance energy transfer (FRET) process to enhance the effective lifetime of organic fluorophores. It was possible to tune the effective lifetime of the fluorophores by about six orders of magnitude from the nanosecond (ns) up to the millisecond (ms) region. Undoped and Mn-doped CdS/ZnS quantum dots functionalized with different dye molecules were selected as a model system for investigating the multiple energy transfer process and the specific interaction between Mn ions and the attached dye molecules. While the lifetime of the free dye molecules was about 5 ns, their linking to undoped CdS/ZnS quantum dots led to a long effective lifetime of about 150 ns, following a non-exponential transient. Manganese-doped core-shell quantum dots further enhanced the long-lasting decay time of the dye to several ms. This opens up a pathway to analyse different fluorophores in the time domain with equal spectral emissions. Such lifetime multiplexing would be an interesting alternative to the commonly used spectral multiplexing in fluorescence detection schemes.

Apparatus and methods for installing, removing and adjusting an inner turbine shell section relative to an outer turbine shell section

DOEpatents

Leach, David; Bergendahl, Peter Allen; Waldo, Stuart Forrest; Smith, Robert Leroy; Phelps, Robert Kim

2001-01-01

A turbine includes upper and lower inner shell sections mounting the nozzles and shrouds and which inner shell is supported by pins secured to a surrounding outer shell. To disassemble the turbine for access to the inner shell sections and rotor, an alignment fixture is secured to the lower outer shell section and has pins engaging the inner shell section. To disassemble the turbine, the inner shell weight is transferred to the lower outer shell section via the alignment fixture and cradle pins. Roller assemblies are inserted through access openings vacated by support pins to permit rotation of the lower inner shell section out of and into the lower outer shell section during disassembly and assembly. The alignment fixture includes adjusting rods for adjusting the inner shell axially, vertically, laterally and about a lateral axis. A roller over-cage is provided to rotate the inner shell and a dummy shell to facilitate assembly and disassembly in the field.

7 CFR 51.2123 - Foreign material.

Code of Federal Regulations, 2012 CFR

2012-01-01

... Standards for Grades of Shelled Almonds Definitions § 51.2123 Foreign material. Foreign material means pieces of shell, hulls or other foreign matter which will not pass through a round opening 8/64 of an...

Recombination of open-f-shell tungsten ions

NASA Astrophysics Data System (ADS)

Krantz, C.; Badnell, N. R.; Müller, A.; Schippers, S.; Wolf, A.

2017-03-01

We review experimental and theoretical efforts aimed at a detailed understanding of the recombination of electrons with highly charged tungsten ions characterised by an open 4f sub-shell. Highly charged tungsten occurs as a plasma contaminant in ITER-like tokamak experiments, where it acts as an unwanted cooling agent. Modelling of the charge state populations in a plasma requires reliable thermal rate coefficients for charge-changing electron collisions. The electron recombination of medium-charged tungsten species with open 4f sub-shells is especially challenging to compute reliably. Storage-ring experiments have been conducted that yielded recombination rate coefficients at high energy resolution and well-understood systematics. Significant deviations compared to simplified, but prevalent, computational models have been found. A new class of ab initio numerical calculations has been developed that provides reliable predictions of the total plasma recombination rate coefficients for these ions.

Scallop-Inspired Shell Engineering of Microparticles for Stable and High Volumetric Capacity Battery Anodes.

PubMed

Zhang, Xinghao; Guo, Ruiying; Li, Xianglong; Zhi, Linjie

2018-06-01

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization and evaluation of uniformly sized core-shell imprinted microspheres for the separation trans-resveratrol from giant knotweed

NASA Astrophysics Data System (ADS)

Zhang, Zhaohui; Liu, Li; Li, Hui; Yao, Shouzhuo

2009-09-01

A novel core-shell molecularly imprinting microspheres (MIMs) with trans-resveratrol as the template molecule; acrylamide (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker, was prepared based on SiO 2 microspheres with surface imprinting technique. These core-shell trans-resveratrol imprinted microspheres were characterized by infrared spectra (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and high performance liquid chromatography (HPLC). The results showed that these core-shell imprinted microspheres, which take on perfect spherical shape with average shell thickness of 150 nm, exhibit especially selective recognition for trans-resveratrol. These imprinted microspheres were applied as solid-phase extraction materials for selective extraction of trans-resveratrol from giant knotweed extracting solution successfully.

Flexible configuration-interaction shell-model many-body solver

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

Johnson, Calvin W.; Ormand, W. Erich; McElvain, Kenneth S.

BIGSTICK Is a flexible configuration-Interaction open-source shell-model code for the many-fermion problem In a shell model (occupation representation) framework. BIGSTICK can generate energy spectra, static and transition one-body densities, and expectation values of scalar operators. Using the built-in Lanczos algorithm one can compute transition probabflity distributions and decompose wave functions into components defined by group theory.

76 FR 18684 - Endangered and Threatened Wildlife and Plants; 12-Month Finding on a Petition To List the...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-04-05

... shell spire, degree of carination (i.e., presence and size of a keel or ridge around the outside whorl of the shell), width of umbilicus (i.e., the ventral opening formed in the center of the whorls), and color (Pilsbry 1939, p. 415). Shell morphology is plastic (variable in response to environmental...

Open source integrated modeling environment Delta Shell

NASA Astrophysics Data System (ADS)

Donchyts, G.; Baart, F.; Jagers, B.; van Putten, H.

2012-04-01

In the last decade, integrated modelling has become a very popular topic in environmental modelling since it helps solving problems, which is difficult to model using a single model. However, managing complexity of integrated models and minimizing time required for their setup remains a challenging task. The integrated modelling environment Delta Shell simplifies this task. The software components of Delta Shell are easy to reuse separately from each other as well as a part of integrated environment that can run in a command-line or a graphical user interface mode. The most components of the Delta Shell are developed using C# programming language and include libraries used to define, save and visualize various scientific data structures as well as coupled model configurations. Here we present two examples showing how Delta Shell simplifies process of setting up integrated models from the end user and developer perspectives. The first example shows coupling of a rainfall-runoff, a river flow and a run-time control models. The second example shows how coastal morphological database integrates with the coastal morphological model (XBeach) and a custom nourishment designer. Delta Shell is also available as open-source software released under LGPL license and accessible via http://oss.deltares.nl.

Initiating Molecular Growth in the Interstellar Medium via Dimeric Complexes of Observed Ions and Molecules

NASA Technical Reports Server (NTRS)

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

2011-01-01

A feasible initiation step for particle growth in the interstellar medium (ISM) is simulated by means of ab quantum chemistry methods. The systems studied are dimer ions formed by pairing nitrogen containing small molecules known to exist in the ISM with ions of unsaturated hydrocarbons or vice versa. Complexation energies, structures of ensuing complexes and electronic excitation spectra of the encounter complexes are estimated using various quantum chemistry methods. Moller-Plesset perturbation theory (MP2, Z-averaged perturbation theory (ZAP2), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)), and density functional theory (DFT) methods (B3LYP) were employed along with the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Two types of complexes are predicted. One type of complex has electrostatic binding with moderate (7-20 kcal per mol) binding energies, that are nonetheless significantly stronger than typical van der Waals interactions between molecules of this size. The other type of complex develops strong covalent bonds between the fragments. Cyclic isomers of the nitrogen containing complexes are produced very easily by ion-molecule reactions. Some of these complexes show intense ultraviolet visible spectra for electronic transitions with large oscillator strengths at the B3LYP, omegaB97, and equations of motion coupled cluster (EOM-CCSD) levels. The open shell nitrogen containing carbonaceous complexes especially exhibit a large oscillator strength electronic transition in the visible region of the electromagnetic spectrum.

High-temperature stability of the hydrate shell of a Na+ cation in a flat nanopore with hydrophobic walls

NASA Astrophysics Data System (ADS)

Shevkunov, S. V.

2017-11-01

The effect of elevated temperature has on the hydrate shell of a singly charged sodium cation inside a flat nanopore with smooth walls is studied using the Monte Carlo method. The free energy and the entropy of vapor molecule attachment are calculated by means of a bicanonical statistical ensemble using a detailed model of interactions. The nanopore has a stabilizing effect on the hydrate shell with respect to fluctuations and a destabilizing effect with respect to complete evaporation. At the boiling point of water, behavior is observed that is qualitatively similar to behavior at room temperature, but with a substantial shift in the vapor pressure and shell size.

Multiple piece turbine airfoil

DOEpatents

Kimmel, Keith D; Wilson, Jr., Jack W.

2010-11-02

A turbine airfoil, such as a rotor blade or a stator vane, for a gas turbine engine, the airfoil formed as a shell and spar construction with a plurality of dog bone struts each mounted within openings formed within the shell and spar to allow for relative motion between the spar and shell in the airfoil chordwise direction while also forming a seal between adjacent cooling channels. The struts provide the seal as well as prevent bulging of the shell from the spar due to the cooling air pressure.

Shell-corona microgels from double interpenetrating networks.

PubMed

Rudyak, Vladimir Yu; Gavrilov, Alexey A; Kozhunova, Elena Yu; Chertovich, Alexander V

2018-04-18

Polymer microgels with a dense outer shell offer outstanding features as universal carriers for different guest molecules. In this paper, microgels formed by an interpenetrating network comprised of collapsed and swollen subnetworks are investigated using dissipative particle dynamics (DPD) computer simulations, and it is found that such systems can form classical core-corona structures, shell-corona structures, and core-shell-corona structures, depending on the subchain length and molecular mass of the system. The core-corona structures consisting of a dense core and soft corona are formed at small microgel sizes when the subnetworks are able to effectively separate in space. The most interesting shell-corona structures consist of a soft cavity in a dense shell surrounded with a loose corona, and are found at intermediate gel sizes; the area of their existence depends on the subchain length and the corresponding mesh size. At larger molecular masses the collapsing network forms additional cores inside the soft cavity, leading to the core-shell-corona structure.

Bandgap Engineering of InP QDs Through Shell Thickness and Composition

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

Dennis, Allison M.; Mangum, Benjamin D.; Piryatinski, Andrei

2012-06-21

Fields as diverse as biological imaging and telecommunications utilize the unique photophysical and electronic properties of nanocrystal quantum dots (NQDs). The development of new NQD compositions promises material properties optimized for specific applications, while addressing material toxicity. Indium phosphide (InP) offers a 'green' alternative to the traditional cadmium-based NQDs, but suffers from extreme susceptibility to oxidation. Coating InP cores with more stable shell materials significantly improves nanocrystal resistance to oxidation and photostability. We have investigated several new InP-based core-shell compositions, correlating our results with theoretical predictions of their optical and electronic properties. Specifically, we can tailor the InP core-shell QDsmore » to a type-I, quasi-type-II, or type-II bandgap structure with emission wavelengths ranging from 500-1300 nm depending on the shell material used (ZnS, ZnSe, CdS, or CdSe) and the thickness of the shell. Single molecule microscopy assessments of photobleaching and blinking are used to correlate NQD properties with shell thickness.« less

Study of lithium cation in water clusters: based on atom-bond electronegativity equalization method fused into molecular mechanics.

PubMed

Li, Xin; Yang, Zhong-Zhi

2005-05-12

We present a potential model for Li(+)-water clusters based on a combination of the atom-bond electronegativity equalization and molecular mechanics (ABEEM/MM) that is to take ABEEM charges of the cation and all atoms, bonds, and lone pairs of water molecules into the intermolecular electrostatic interaction term in molecular mechanics. The model allows point charges on cationic site and seven sites of an ABEEM-7P water molecule to fluctuate responding to the cluster geometry. The water molecules in the first sphere of Li(+) are strongly structured and there is obvious charge transfer between the cation and the water molecules; therefore, the charge constraint on the ionic cluster includes the charged constraint on the Li(+) and the first-shell water molecules and the charge neutrality constraint on each water molecule in the external hydration shells. The newly constructed potential model based on ABEEM/MM is first applied to ionic clusters and reproduces gas-phase state properties of Li(+)(H(2)O)(n) (n = 1-6 and 8) including optimized geometries, ABEEM charges, binding energies, frequencies, and so on, which are in fair agreement with those measured by available experiments and calculated by ab initio methods. Prospects and benefits introduced by this potential model are pointed out.

The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation

DOE PAGES

Skinner, L. B.; Galib, M.; Fulton, J. L.; ...

2016-04-04

In this study, x-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å 3. The measurements were conducted at a spatial resolution corresponding to Q max = 16 Å -1. The method of data analysis and measurement in this study follows the earlier benchmark results reported for water under ambient conditions having a density of 0.0333 molecules per Å 3 and Q max = 20 Å -1 [J. Chem. Phys. 138, 074506 (2013)] and at 70°C having a density of 0.0327 molecules per Å 3 and Qmore » max = 20 Å -1 [J. Chem. Phys. 141, 214507 (2014)]. The structure of water is very different at these three different T and P state points and thus they provide the basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3 and 3 Å are nearly unchanged: the peak position, shape, and coordination number are nearly identical to their values under ambient conditions. However, in the region above 3 Å, large structural changes occur with the collapse of the well-defined 2nd shell and shifting of higher shells to shorter distances. The measured structure is compared to simulated structure using intermolecular potentials described by both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005, MB-pol, and mW). The DFT-based, revPBE-D3, method and the many-body empirical potential model, MB-pol, provide the best overall representation of the ambient, high-temperature, and high-pressure data. Finally, the revPBE-D3, MB-pol, and the TIP4P/2005 models capture the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which partially encroaches the 1st shell at ambient pressure, is pushed further into the local tetrahedral arrangement at higher pressures by the more distant molecules filling the void space in the network between the 1st and 2nd shells.« less

Synthesis and characterization of core-shell gold nanoparticles with poly(vinyl pyrrolidone) from a new precursor salt

NASA Astrophysics Data System (ADS)

Behera, M.; Ram, S.

2013-02-01

In this article, we report a facile one-step chemical synthesis of gold (Au) nanoparticles (GNPs) from a new precursor salt i.e., gold hydroxide in the presence of poly(vinyl pyrrolidone) (PVP) polymer. The non-aqueous dispersion of GNPs was comprehensively characterized by UV-Visible, FTIR, zeta potential, and transmission electron microscope (TEM). A strong surface plasmon resonance band at 529 nm in the UV-Visible spectrum confirms the formation of GNPs in the Au colloid. The FTIR spectroscopic results showed that PVP molecules get chemisorbed onto the surface of GNP via O-atom of carbonyl group. A negative zeta potential of (-)16 mV reveals accumulation of nonbonding electrons of O-atom of carbonyl group of PVP molecules on the nanosurface of GNP. TEM images demonstrate a core-shell nanostructure with an Au-crystalline core covered by a thin amorphous PVP-shell. PVP-capped GNPs could be a potential candidate for bio-sensing, catalysis, and other applications.

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

PubMed

Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

2016-05-02

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

Binding Preferences of Amino Acids for Gold Nanoparticles: A Molecular Simulation Study.

PubMed

Shao, Qing; Hall, Carol K

2016-08-09

A better understanding of the binding preference of amino acids for gold nanoparticles of different diameters could aid in the design of peptides that bind specifically to nanoparticles of a given diameter. Here we identify the binding preference of 19 natural amino acids for three gold nanoparticles with diameters of 1.0, 2.0, and 4.0 nm, and investigate the mechanisms that govern these preferences. We calculate potentials of mean force between 36 entities (19 amino acids and 17 side chains) and the three gold nanoparticles in explicit water using well-tempered metadynamics simulations. Comparing these potentials of mean force determines the amino acids' nanoparticle binding preferences and if these preferences are controlled by the backbone, the side chain, or both. Twelve amino acids prefer to bind to the 4.0 nm gold nanoparticle, and seven prefer to bind to the 2.0 nm one. We also use atomistic molecular dynamics simulations to investigate how water molecules near the nanoparticle influence the binding of the amino acids. The solvation shells of the larger nanoparticles have higher water densities than those of the smaller nanoparticles while the orientation distributions of the water molecules in the shells of all three nanoparticles are similar. The nanoparticle preferences of the amino acids depend on whether their binding free energy is determined mainly by their ability to replace or to reorient water molecules in the nanoparticle solvation shell. The amino acids whose binding free energy depends mainly on the replacement of water molecules are likely to prefer to bind to the largest nanoparticle and tend to have relatively simple side chain structures. Those whose binding free energy depends mainly on their ability to reorient water molecules prefer a smaller nanoparticle and tend to have more complex side chain structures.

Quantitative analysis of curcumin-loaded alginate nanocarriers in hydrogels using Raman and attenuated total reflection infrared spectroscopy.

PubMed

Miloudi, Lynda; Bonnier, Franck; Bertrand, Dominique; Byrne, Hugh J; Perse, Xavier; Chourpa, Igor; Munnier, Emilie

2017-07-01

Core-shell nanocarriers are increasingly being adapted in cosmetic and dermatological fields, aiming to provide an increased penetration of the active pharmaceutical or cosmetic ingredients (API and ACI) through the skin. In the final form, the nanocarriers (NC) are usually prepared in hydrogels, conferring desired viscous properties for topical application. Combined with the high chemical complexity of the encapsulating system itself, involving numerous ingredients to form a stable core and quantifying the NC and/or the encapsulated active without labor-intensive and destructive methods remains challenging. In this respect, the specific molecular fingerprint obtained from vibrational spectroscopy analysis could unambiguously overcome current obstacles in the development of fast and cost-effective quality control tools for NC-based products. The present study demonstrates the feasibility to deliver accurate quantification of the concentrations of curcumin (ACI)-loaded alginate nanocarriers in hydrogel matrices, coupling partial least square regression (PLSR) to infrared (IR) absorption and Raman spectroscopic analyses. With respective root mean square errors of 0.1469 ± 0.0175% w/w and 0.4462 ± 0.0631% w/w, both approaches offer acceptable precision. Further investigation of the PLSR results allowed to highlight the different selectivity of each approach, indicating only IR analysis delivers direct monitoring of the NC through the quantification of the Labrafac®, the main NC ingredient. Raman analyses are rather dominated by the contribution of the ACI which opens numerous perspectives to quantify the active molecules without interferences from the complex core-shell encapsulating systems thus positioning the technique as a powerful analytical tool for industrial screening of cosmetic and pharmaceutical products. Graphical abstract Quantitative analysis of encapuslated active molecules in hydrogel-based samples by means of infrared and Raman spectroscopy.

Exploring Early Stages of the Chemical Unfolding of Proteins at the Proteome Scale

PubMed Central

Candotti, Michela; Pérez, Alberto; Ferrer-Costa, Carles; Rueda, Manuel; Meyer, Tim; Gelpí, Josep Lluís; Orozco, Modesto

2013-01-01

After decades of using urea as denaturant, the kinetic role of this molecule in the unfolding process is still undefined: does urea actively induce protein unfolding or passively stabilize the unfolded state? By analyzing a set of 30 proteins (representative of all native folds) through extensive molecular dynamics simulations in denaturant (using a range of force-fields), we derived robust rules for urea unfolding that are valid at the proteome level. Irrespective of the protein fold, presence or absence of disulphide bridges, and secondary structure composition, urea concentrates in the first solvation shell of quasi-native proteins, but with a density lower than that of the fully unfolded state. The presence of urea does not alter the spontaneous vibration pattern of proteins. In fact, it reduces the magnitude of such vibrations, leading to a counterintuitive slow down of the atomic-motions that opposes unfolding. Urea stickiness and slow diffusion is, however, crucial for unfolding. Long residence urea molecules placed around the hydrophobic core are crucial to stabilize partially open structures generated by thermal fluctuations. Our simulations indicate that although urea does not favor the formation of partially open microstates, it is not a mere spectator of unfolding that simply displaces to the right of the folded←→unfolded equilibrium. On the contrary, urea actively favors unfolding: it selects and stabilizes partially unfolded microstates, slowly driving the protein conformational ensemble far from the native one and also from the conformations sampled during thermal unfolding. PMID:24348236

Stabilizing effects of hydrated fullerenes C₆₀ in a wide range of concentrations on luciferase, alkaline phosphatase, and peroxidase in vitro.

PubMed

Voeikov, Vladimir L; Yablonskaya, Olga I

2015-01-01

Hydrated fullerene (HyFnC60) is a highly hydrophilic supra-molecular complex consisting of unmodified С60 fullerene molecule enclosed into a hydrated shell. It has been shown in numerous experiments that aqueous solutions of HyFnC60 manifest a wide range of biological activities both in vivo and in vitro even at very low concentrations of HyFnC60. We used a spectrophotometric method and a method of biochemoluminescence to demonstrate that HyFnC60 in concentrations below 10(-9) M down to 10(-23) M stabilizes peroxidase, alkaline phosphatase, and bacterial luciferase against inactivation due to long-term incubation of the enzymes at room temperature and also against heat inactivation. In addition, HyFnC60 was able to "revive" heat inactivated enzymes. These effects cannot be explained by the direct action of the fullerene molecules upon the enzymes. We suggest that the effects of HyFnC60 on the enzymes are related to the ability of hydrated fullerene C60 molecules to organize thick aqueous shells around them. One of the specific properties of water phase in these shells is its ability to optimize redox reactions, which can support enzyme stability against factors deteriorating their structure.

Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

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

Tian, Yong-Hui; Sumpter, Bobby G.; Du, Shiyu

Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap ismore » distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.« less

Pancake π–π Bonding Goes Double: Unexpected 4e/All-Sites Bonding in Boron- and Nitrogen-Doped Phenalenyls

DOE PAGES

Tian, Yong-Hui; Sumpter, Bobby G.; Du, Shiyu; ...

2015-06-03

Phenalenyl is an important neutral pi-radical due to its capability to form unconventional pancake pi-pi bonding interactions, whereas its analogues with graphitic boron (B) or nitrogen (N)-doping have been regarded as closed-shell systems and therefore received much less attention. By using high-level quantum chemistry calculations, we also show that the B- and N-doped closed-shell phenalenyls unexpectedly form open-shell singlet pi-dimers with diradicaloid character featuring 2e/all-sites double pi-pi bonding. Moreover, by proper substitutions, the doped phenalenyl derivatives can be made open-shell species that form closed shell singlet pi-dimers bound by stronger 4e/all-sites double pi-pi bonding. Moreover, covalent pi-pi bonding overlap ismore » distributed on all of the atomic sites giving robust and genuine pancake-shaped pi-dimers which, depending on the number of electrons available in the bonding interactions, are equally or more stable than the pi-dimers of the pristine phenalenyl.« less

Emission Behavior of Fluorescently Labeled Silver Nanoshell: Enhanced Self-Quenching by Metal Nanostructure.

PubMed

Zhang, Jian; Fu, Yi; Lakowicz, Joseph R

2007-02-08

Labeled silica beads with an average diameter of 100 nm were synthesized by incorporating with 20-600 μM Ru(bpy)(3) (2+) complexes. Silver shells were deposited on the beads layer-by-layer with the shell thickness of 5-50 nm. The emission band became narrower and the intensity was enhanced depending on the shell thickness. Self-quenching of the probe was observed at high concentration. Poisson statistics were employed to analyze self-quenching of the fluorophores. The estimated quenching distance was extended from 6 to 16 nm with shell growth from 0 to 50 nm. Moreover, the silver shells were also labeled with Rhodamine 6G. Fluorescence enhancement and reduced lifetime were also observed for silver-silica shell containing R6G. We found that by adjustment of probe concentration and silver shell thickness, a Ru(bpy)(3) (2+)-labeled particle could be 600 times brighter than an isolated Ru(bpy)(3) (2+) molecule. We expect labeled metal core-shell structures can become useful probes for high sensitivity and/or single particle assay.

Authentic Assessment Tool for the Measurement of Students' Understanding of the Valence Shell Electron Pair Repulsion Theory

ERIC Educational Resources Information Center

Wuttisela, Karntarat

2017-01-01

There are various types of instructional media related to Valence Shell Electron Pair Repulsion (VSEPR) but there is a lack of diversity of resources devoted to assessment. This research presents an assessment and comparison of students' understanding of VSEPR theory before and after tuition involving the use of the foam molecule model (FMM) and…

Investigations of the Interactions of Radiation with Matter.

DTIC Science & Technology

1986-07-31

Process in Atoms, Molecules and Solids, eds. A. Mei-el and J. Finster , (Karl-Marx Universitat, Leipzig, 1984), p. 58. 10. S.T. Manson in High Enery Ion...H. Toburen, and S. T. Manson in X-Ra and Inner-Shell Process in Atoms, Molecules and Solids, eds. A. Meisel and J. Finster , (Karl-Marx- Universitat

Biosensing via light scattering from plasmonic core-shell nanospheres coated with DNA molecules

NASA Astrophysics Data System (ADS)

Xie, Huai-Yi; Chen, Minfeng; Chang, Yia-Chung; Moirangthem, Rakesh Singh

2017-05-01

We present both experimental and theoretical studies for investigating DNA molecules attached on metallic nanospheres. We have developed an efficient and accurate numerical method to investigate light scattering from plasmonic nanospheres on a substrate covered by a shell, based on the Green's function approach with suitable spherical harmonic basis. Next, we use this method to study optical scattering from DNA molecules attached to metallic nanoparticles placed on a substrate and compare with experimental results. We obtain fairly good agreement between theoretical predictions and the measured ellipsometric spectra. The metallic nanoparticles were used to detect the binding with DNA molecules in a microfluidic setup via spectroscopic ellipsometry (SE), and a detectable change in ellipsometric spectra was found when DNA molecules are captured on Au nanoparticles. Our theoretical simulation indicates that the coverage of Au nanosphere by a submonolayer of DNA molecules, which is modeled by a thin layer of dielectric material (which may absorb light), can lead to a small but detectable spectroscopic shift in both the Ψ and Δ spectra with more significant change in Δ spectra in agreement with experimental results. Our studies demonstrated the ultrasensitive capability of SE for sensing submonolayer coverage of DNA molecules on Au nanospheres. Hence the spectroscopic ellipsometric measurements coupled with theoretical analysis via an efficient computation method can be an effective tool for detecting DNA molecules attached on Au nanoparticles, thus achieving label-free, non-destructive, and high-sensitivity biosensing with nanoscale resolution.

Metal coated colloidosomes as carriers for an antibiotic

NASA Astrophysics Data System (ADS)

Sun, Qian; Zhao, Ziyan; Hall, Elizabeth A. H.; Routh, Alexander F.

2018-06-01

Colloidosomes are polymer shell microcapsules. They are stable and easy to prepare and have been used to encapsulate drugs for release at specific areas in the body. Traditional polymer shell capsules cannot totally seal drugs, since they are porous and small molecules diffuse through the polymer shell. In this paper, we report a method for encapsulating an antibiotic kanamycin using gold or silver coated colloidosomes. The colloidosomes are impermeable and can be triggered using ultrasound. To investigate the application of the capsules in a biological system, Escherichia Coli (E.coli) was chosen as a model organism. After triggering, the released antibiotic, as well as the metal shell fragments, kill E.coli. Both the silver and gold shells colloidosomes are toxic to this bacterial system and the gold coated colloidosomes can load a higher concentration of kanamycin.

Biomimetic synthesis of raspberry-like hybrid polymer-silica core-shell nanoparticles by templating colloidal particles with hairy polyamine shell.

PubMed

Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan

2010-07-01

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.

Open sd-shell nuclei from first principles

DOE PAGES

Jansen, Gustav R.; Signoracci, Angelo J.; Hagen, Gaute; ...

2016-07-05

We extend the ab initio coupled-cluster effective interaction (CCEI) method to open-shell nuclei with protons and neutrons in the valence space, and compute binding energies and excited states of isotopes of neon and magnesium. We employ a nucleon-nucleon and three-nucleon interaction from chiral effective field theory evolved to a lower cutoff via a similarity renormalization group transformation. We find good agreement with experiment for binding energies and spectra, while charge radii of neon isotopes are underestimated. For the deformed nuclei 20Ne and 24Mg we reproduce rotational bands and electric quadrupole transitions within uncertainties estimated from an effective field theory formore » deformed nuclei, thereby demonstrating that collective phenomena in sd-shell nuclei emerge from complex ab initio calculations.« less

Open sd-shell nuclei from first principles

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

Jansen, Gustav R.; Signoracci, Angelo J.; Hagen, Gaute

We extend the ab initio coupled-cluster effective interaction (CCEI) method to open-shell nuclei with protons and neutrons in the valence space, and compute binding energies and excited states of isotopes of neon and magnesium. We employ a nucleon-nucleon and three-nucleon interaction from chiral effective field theory evolved to a lower cutoff via a similarity renormalization group transformation. We find good agreement with experiment for binding energies and spectra, while charge radii of neon isotopes are underestimated. For the deformed nuclei 20Ne and 24Mg we reproduce rotational bands and electric quadrupole transitions within uncertainties estimated from an effective field theory formore » deformed nuclei, thereby demonstrating that collective phenomena in sd-shell nuclei emerge from complex ab initio calculations.« less

Photoionization cross sections for atomic chlorine using an open-shell random phase approximation

NASA Technical Reports Server (NTRS)

Starace, A. F.; Armstrong, L., Jr.

1975-01-01

The use of the Random Phase Approximation with Exchange (RPAE) for calculating partial and total photoionization cross sections and photoelectron angular distributions for open shell atoms is examined for atomic chlorine. Whereas the RPAE corrections in argon (Z=18) are large, it is found that those in chlorine (Z=17) are much smaller due to geometric factors. Hartree-Fock calculations with and without core relaxation are also presented. Sizable deviations from the close coupling results of Conneely are also found.

H{sub 2} MOLECULAR CLUSTERS WITH EMBEDDED MOLECULES AND ATOMS AS THE SOURCE OF THE DIFFUSE INTERSTELLAR BANDS

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

Bernstein, L. S.; Clark, F. O.; Lynch, D. K., E-mail: larry@spectral.com, E-mail: dave@thulescientific.com

2013-05-01

We suggest that the diffuse interstellar bands (DIBs) arise from absorption lines of electronic transitions in molecular clusters primarily composed of a single molecule, atom, or ion ({sup s}eed{sup )}, embedded in a single-layer shell of H{sub 2} molecules. Less abundant variants of the cluster, including two seed molecules and/or a two-layer shell of H{sub 2} molecules, may also occur. The lines are broadened, blended, and wavelength-shifted by interactions between the seed and surrounding H{sub 2} shell. We refer to these clusters as contaminated H{sub 2} clusters (CHCs). We show that CHC spectroscopy matches the diversity of observed DIB spectralmore » profiles and provides good fits to several DIB profiles based on a rotational temperature of 10 K. CHCs arise from {approx}centimeter-sized, dirty H{sub 2} ice balls, called contaminated H{sub 2} ice macro-particles (CHIMPs), formed in cold, dense, giant molecular clouds (GMCs), and later released into the interstellar medium (ISM) upon GMC disruption. Attractive interactions, arising from Van der Waals and ion-induced dipole potentials, between the seeds and H{sub 2} molecules enable CHIMPs to attain centimeter-sized dimensions. When an ultraviolet (UV) photon is absorbed in the outer layer of a CHIMP, it heats the icy matrix and expels CHCs into the ISM. While CHCs are quickly destroyed by absorbing UV photons, they are replenished by the slowly eroding CHIMPs. Since CHCs require UV photons for their release, they are most abundant at, but not limited to, the edges of UV-opaque molecular clouds, consistent with the observed, preferred location of DIBs. An inherent property of CHCs, which can be characterized as nanometer size, spinning, dipolar dust grains, is that they emit in the radio-frequency region. We also show that the CHCs offer a natural explanation for the anomalous microwave emission feature in the {approx}10-100 GHz spectral region.« less

The influence of shell thickness of Au@TiO2 core-shell nanoparticles on the plasmonic enhancement effect in dye-sensitized solar cells.

PubMed

Liu, Wei-Liang; Lin, Fan-Cheng; Yang, Yu-Chen; Huang, Chen-Hsien; Gwo, Shangjr; Huang, Michael H; Huang, Jer-Shing

2013-09-07

Plasmonic core-shell nanoparticles (PCSNPs) can function as nanoantennas and improve the efficiency of dye-sensitized solar cells (DSSCs). To achieve maximum enhancement, the morphology of PCSNPs needs to be optimized. Here we precisely control the morphology of Au@TiO2 PCSNPs and systematically study its influence on the plasmonic enhancement effect. The enhancement mechanism was found to vary with the thickness of the TiO2 shell. PCSNPs with a thinner shell mainly enhance the current, whereas particles with a thicker shell improve the voltage. While pronounced plasmonic enhancement was found in the near infrared regime, wavelength-independent enhancement in the visible range was observed and attributed to the plasmonic heating effect. Emission lifetime measurement confirms that N719 molecules neighboring nanoparticles with TiO2 shells exhibit a longer lifetime than those in contact with metal cores. Overall, PCSNPs with a 5 nm shell give the highest efficiency enhancement of 23%. Our work provides a new synthesis route for well-controlled Au@TiO2 core-shell nanoparticles and gains insight into the plasmonic enhancement in DSSCs.

Ab initio Bogoliubov coupled cluster theory for open-shell nuclei

DOE PAGES

Signoracci, Angelo J.; Duguet, Thomas; Hagen, Gaute; ...

2015-06-29

Background: Ab initio many-body methods have been developed over the past 10 yr to address closed-shell nuclei up to mass A≈130 on the basis of realistic two- and three-nucleon interactions. A current frontier relates to the extension of those many-body methods to the description of open-shell nuclei. Several routes to address open-shell nuclei are currently under investigation, including ideas that exploit spontaneous symmetry breaking. Purpose: Singly open-shell nuclei can be efficiently described via the sole breaking of U(1) gauge symmetry associated with particle-number conservation as a way to account for their superfluid character. While this route was recently followed withinmore » the framework of self-consistent Green's function theory, the goal of the present work is to formulate a similar extension within the framework of coupled cluster theory. Methods: We formulate and apply Bogoliubov coupled cluster (BCC) theory, which consists of representing the exact ground-state wave function of the system as the exponential of a quasiparticle excitation cluster operator acting on a Bogoliubov reference state. Equations for the ground-state energy and the cluster amplitudes are derived at the singles and doubles level (BCCSD) both algebraically and diagrammatically. The formalism includes three-nucleon forces at the normal-ordered two-body level. The first BCC code is implemented in m scheme, which will permit the treatment of doubly open-shell nuclei via the further breaking of SU(2) symmetry associated with angular momentum conservation. Results: Proof-of-principle calculations in an N max=6 spherical harmonic oscillator basis for 16,18O and 18Ne in the BCCD approximation are in good agreement with standard coupled cluster results with the same chiral two-nucleon interaction, while 20O and 20Mg display underbinding relative to experiment. The breaking of U(1) symmetry, monitored by computing the variance associated with the particle-number operator, is relatively constant for all five nuclei, in both the Hartree-Fock-Bogoliubov and BCCD approximations. Conclusions: The newly developed many-body formalism increases the potential span of ab initio calculations based on single-reference coupled cluster techniques tremendously, i.e., potentially to reach several hundred additional midmass nuclei. The new formalism offers a wealth of potential applications and further extensions dedicated to the description of ground and excited states of open-shell nuclei. Short-term goals include the implementation of three-nucleon forces at the normal-ordered two-body level. Midterm extensions include the approximate treatment of triples corrections and the development of the equation-of-motion methodology to treat both excited states and odd nuclei. Long-term extensions include exact restoration of U(1) and SU(2) symmetries.« less

Theoretical study of the vibrational relaxation of the methyl radical in collisions with helium

NASA Astrophysics Data System (ADS)

Ma, Qianli; Dagdigian, Paul J.; Alexander, Millard H.

2013-03-01

We report a theoretical investigation of the relaxation of the umbrella vibrational mode (the ν2 mode) of the CH3 molecule in its ground tilde{X}^2A_2^' ' } electronic state in collisions with helium. We have calculated a four-dimensional potential energy surface (PES) for the interaction between CH3 with different umbrella displacements and a helium atom, using a restricted open-shell coupled-cluster method with inclusion of all single, double, and (perturbatively) triple excitations [RCCSD(T)]. With this PES we carried out full close-coupling scattering calculations including all CH3 umbrella-rotational levels with v2 ⩽ 3. To our knowledge, this work represents the first fully quantum calculations of ro-vibrational relaxation of a polyatomic. In more detail, we investigate propensities in the calculated ro-vibrational cross sections and the dependence on initial rotational excitation, as well as determining thermal rate constants. Overall, ro-vibrational relaxation is nearly two orders of magnitude less efficient than pure-rotational relaxation, with a noticeable dependence on the initial rotational level. We predict the room temperature v2 = 1 vibrational relaxation rate constant to be 5.4 × 10-12 cm3 molecule-1 s-1, compared to the rate constants for pure-rotational relaxation of the lower rotational levels (˜2.0 × 10-10 cm3 molecule-1 s-1).

Formation of Core-Shell Ethane-Silver Clusters in He Droplets.

PubMed

Loginov, Evgeny; Gomez, Luis F; Sartakov, Boris G; Vilesov, Andrey F

2017-08-17

Ethane core-silver shell clusters consisting of several thousand particles have been assembled in helium droplets upon capture of ethane molecules followed by Ag atoms. The composite clusters were studied via infrared laser spectroscopy in the range of the C-H stretching vibrations of ethane. The spectra reveal a splitting of the vibrational bands, which is ascribed to interaction with Ag. A rigorous analysis of band intensities for a varying number of trapped ethane molecules and Ag atoms indicates that the composite clusters consist of a core of ethane that is covered by relatively small Ag clusters. This metastable structure is stabilized due to fast dissipation in superfluid helium droplets of the cohesion energy of the clusters.

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

Gomez, John A.; Henderson, Thomas M.; Scuseria, Gustavo E.

Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior formore » strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.« less

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

DOE PAGES

Garg, Aaron; Milina, Maria; Ball, Madelyn; ...

2017-05-25

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts

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

Garg, Aaron; Milina, Maria; Ball, Madelyn

Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less

Chromocene in porous polystyrene: an example of organometallic chemistry in confined spaces.

PubMed

Estephane, Jane; Groppo, Elena; Vitillo, Jenny G; Damin, Alessandro; Lamberti, Carlo; Bordiga, Silvia; Zecchina, Adriano

2009-04-07

In this work, we present an innovative approach to investigate the structure and the reactivity of a molecularly dispersed organometallic compound. The poly(4-ethylstyrene-co-divinylbenzene) microporous system (PS) is used as "solid solvent" able to molecularly disperse CrCp2, allowing: (i) its full characterization by means of spectroscopic techniques; (ii) the pressure and temperature dependent study of its interaction towards simple molecules like CO freely diffusing through the pores; (iii) the accurate determination of the reaction enthalpies by both direct microcalorimetric measurements and by an indirect spectroscopic approach. The experimental results are compared with quantum-mechanical calculations adopting the DFT approximation with two different functionals (namely BP86 and B3-LYP), showing the limitations and the potentialities of DFT methods in predicting the properties of open shell systems. It is concluded that modern DFT methods are able to give a coherent view of the vibrational properties of the CrCp2 molecule (and of the complex formed upon CO adsorption) that well match the experimental results, while the energetic predictions should be taken with care as they are significantly dependent on the functionals used.

Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks

DOE PAGES

Ongari, Daniele; Tiana, Davide; Stoneburner, Samuel J.; ...

2017-06-27

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireferencemore » wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.« less

Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks.

PubMed

Ongari, Daniele; Tiana, Davide; Stoneburner, Samuel J; Gagliardi, Laura; Smit, Berend

2017-07-20

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper-CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2 (formate) 4 . We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2 , even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller-Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.

Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks

PubMed Central

2017-01-01

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate)2 and dicopper Cu2(formate)4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO2, even including corrections for the dispersion forces. In contrast, a multireference wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems. PMID:28751926

Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks

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

Ongari, Daniele; Tiana, Davide; Stoneburner, Samuel J.

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally. In this work we investigate the copper–CO 2 interaction in HKUST-1 and in two different cluster models of HKUST-1: monocopper Cu(formate) 2 and dicopper Cu 2(formate) 4. We show that density functional theory methods severely underestimate the interaction energy between copper paddle-wheels and CO 2, even including corrections for the dispersion forces. In contrast, a multireferencemore » wave function followed by perturbation theory to second order using the CASPT2 method correctly describes this interaction. The restricted open-shell Møller–Plesset 2 method (ROS-MP2, equivalent to (2,2) CASPT2) was also found to be adequate in describing the system and used to develop a novel force field. Our parametrization is able to predict the experimental CO 2 adsorption isotherms in HKUST-1, and it is shown to be transferable to other copper paddle-wheel systems.« less

High Resolution Spectroscopy and Dynamics: from Jet Cooled Radicals to Gas-Liquid Interfaces

NASA Astrophysics Data System (ADS)

Sharp-Williams, E.; Roberts, M. A.; Roscioli, J. R.; Gisler, A. W.; Ziemkiewicz, M.; Nesbitt, D. J.; Dong, F.; Perkins, B. G., Jr.

2010-06-01

This talk will attempt to reflect recent work in our group involving two quite different but complementary applications of high resolution molecular spectroscopy for detailed study of intramolecular as well as intermolecular dynamics in small molecules. The first is based on direct infrared absorption spectroscopy in a 100 KHz slit supersonic discharge, which provides a remarkably versatile and yet highly sensitive probe for study of important chemical transients such as open shell combustion species and molecular ions under jet cooled (10-20K), sub-Doppler conditions. For this talk will focus on gas phase spectroscopic results for a series of unsaturated hydrocarbon radical species (ethynyl, vinyl, and phenyl) reputed to be critical intermediates in soot formation. Secondly, we will discuss recent applications of high resolution IR and velocity map imaging spectroscopy toward quantum state resolved collision dynamics of jet cooled molecules from gas-room temperature ionic liquid (RTIL) and gas-self assembled monolayer (SAM) interfaces. Time permitting, we will also present new results on hyperthermal scattering of jet cooled NO radical from liquid Ga, which offer a novel window into non-adiabatic energy transfer and electron-hole pair dynamics at the gas-molten metal interface.

Carbon-Coated Gold Nanorods: A Facile Route to Biocompatible Materials for Photothermal Applications.

PubMed

Kaneti, Yusuf Valentino; Chen, Chuyang; Liu, Minsu; Wang, Xiaochun; Yang, Jia Lin; Taylor, Robert Allen; Jiang, Xuchuan; Yu, Aibing

2015-11-25

Gold nanorods and their core-shell nanocomposites have been widely studied because of their well-defined anisotropy and unique optical properties and applications. This study demonstrates a facile hydrothermal synthesis strategy for generating carbon coating on gold nanorods (AuNRs@C) under mild conditions (<200 °C), where the carbon shell is composed of polymerized sugar molecules (glucose). The structure and composition of the produced core-shell nanocomposites were characterized using advanced microscopic and spectroscopic techniques. The functional properties, particularly the photothermal and biocompatibility properties of the produced AuNRs@C, were quantified to assess their potential in photothermal hyperthermia. These AuNRs@C were tested in vitro (under representative treatment conditions) using near-infrared (NIR) light irradiation. It was found that the AuNRs produced here exhibit exemplary heat generation capability. Temperature changes of 10.5, 9, and 8 °C for AuNRs@C were observed with carbon shell thicknesses of 10, 17, and 25 nm, respectively, at a concentration of 50 μM, after 600 s of irradiation with a laser power of 0.17 W/cm(2). In addition, the synthesized AuNRs@C also exhibit good biocompatibility toward two soft tissue sarcoma cell lines (HT1080, a fibrosarcoma; and GCT, a fibrous histiocytoma). The cell viability study shows that AuNRs@C (at a concentration of <0.1 mg/mL) core-shell particles induce significantly lower cytotoxicity on both HT1080 and GCT cell lines, as compared with cetyltrimethylammonium bromide (CTAB)-capped AuNRs. Furthermore, similar to PEG-modified AuNRs, they are also safe to both HT1080 and GCT cell lines. This biocompatibility results from a surface full of -OH or -COH groups, which are suitable for linking and are nontoxic Therefore, the AuNRs@C represent a viable alternative to PEG-coated AuNRs for facile synthesis and improved photothermal conversion. Overall, these findings open up a new class of carbon-coated nanostructures that are biocompatible and could potentially be employed in a wide range of biomedical applications.

Free vibration of laminated composite stiffened hyperbolic paraboloid shell panel with cutout

NASA Astrophysics Data System (ADS)

Sahoo, Sarmila

2016-08-01

Composite shell structures are extensively used in aerospace, civil, marine and other engineering applications. In practical civil engineering applications, the necessity of covering large column free open areas is often an issue and hyperbolic paraboloid shells are used as roofing units. Quite often, to save weight and also to provide a facility for inspection, cutouts are provided in shell panels. The paper considers free vibration characteristics of stiffened composite hyperbolic paraboloid shell panel with cutout in terms of natural frequency and mode shapes. A finite element code is developed for the purpose by combining an eight noded curved shell element with a three noded curved beam element. The size of the cutouts and their positions with respect to the shell centre are varied for different edge conditions to arrive at a set of inferences of practical engineering significances.

Improved open-circuit voltage in polymer/oxide-nanoarray hybrid solar cells by formation of homogeneous metal oxide core/shell structures.

PubMed

Wu, Fan; Cui, Qi; Qiu, Zeliang; Liu, Changwen; Zhang, Hui; Shen, Wei; Wang, Mingtai

2013-04-24

Incorporation of vertically aligned nanorod/nanowire arrays of metal oxide (oxide-NAs) with a polymer can produce efficient hybrid solar cells with an ideal bulk-heterojunction architecture. However, polymer/oxide-NAs solar cells still suffer from a rather low (normally, < 0.4 V) open-circuit voltage (Voc). Here we demonstrate, for the first time, a novel strategy to improve the Voc in polymer/oxide-NAs solar cells by formation of homogeneous core/shell structures and reveal the intrinsic principles involved therein. A feasible hydrothermal-solvothermal combined method is developed for preparing homogeneous core/shell nanoarrays of metal oxides with a single-crystalline nanorod as core and the aggregation layer of corresponding metal oxide quantum dots (QDs) as shell, and the shell thickness (L) is easily controlled by the solvothermal reaction time for growing QDs on the nanorod. The core/shell formation dramatically improves the device Voc up to ca. 0.7-0.8 V depending on L. Based on steady-state and dynamic measurements, as well as modeling by space-charge-limited current method, it is found that the improved Voc originates from the up-shifted conduction band edge in the core by the interfacial dipole field resulting from the decreased mobility difference between photogenerated electrons and holes after the shell growth, which increases the energy difference between the quasi-Fermi levels of photogenerated electrons in the core and holes in the polymer for a higher Voc. Our results indicate that increasing Voc by the core/shell strategy seems not to be dependent on the kinds of metal oxides.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture

NASA Astrophysics Data System (ADS)

Spickermann, C.; Thar, J.; Lehmann, S. B. C.; Zahn, S.; Hunger, J.; Buchner, R.; Hunt, P. A.; Welton, T.; Kirchner, B.

2008-09-01

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C2C1im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C2C1im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H2O )-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C2C1im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Why are ionic liquid ions mainly associated in water? A Car-Parrinello study of 1-ethyl-3-methyl-imidazolium chloride water mixture.

PubMed

Spickermann, C; Thar, J; Lehmann, S B C; Zahn, S; Hunger, J; Buchner, R; Hunt, P A; Welton, T; Kirchner, B

2008-09-14

In this study we present the results of a first principles molecular dynamics simulation of a single 1-ethyl-3-methyl-imidazolium chloride [C(2)C(1)im][Cl] ion pair dissolved in 60 water molecules. We observe a preference of the in plane chloride coordination with respect to the cation ring plane as compared to the energetic slightly more demanding on top coordination. Evaluation of the different radial distribution functions demonstrates that the structure of the hydration shell around the ion pair differs significantly from bulk water and that no true ion pair dissociation in terms of completely autonomous solvation shells takes place on the timescale of the simulation. In addition, dipole moment distributions of the solvent in distinct solvation shells around different functional parts of the [C(2)C(1)im][Cl] ion pair are calculated from maximally localized Wannier functions. The analysis of these distributions gives evidence for a depolarization of water molecules close to the hydrophobic parts of the cation as well as close to the anion. Examination of the angular distribution of different OH(H(2)O)-X angles in turn shows a linear coordination of chloride accompanied by a tangential orientation of water molecules around the hydrophobic groups, being a typical feature of hydrophobic hydration. Based on these orientational aspects, a structural model for the obvious preference of ion pair association is developed, which justifies the associating behavior of solvated [C(2)C(1)im][Cl] ions in terms of an energetically favorable interface between the solvation shells of the anion and the hydrophobic parts of the cation.

Modeling the interactions of phthalocyanines in water: from the Cu(II)-tetrasulphonate to the metal-free phthalocyanine.

PubMed

Martín, Elisa I; Martínez, Jose M; Sánchez Marcos, Enrique

2011-01-14

A quantum and statistical study on the effects of the ions Cu(2+) and SO(3)(-) in the solvent structure around the metal-free phthalocyanine (H(2)Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H(2)O based on quantum chemical calculations and studied its transferability to the H(2)Pc-H(2)O and [CuPc(SO(3))(4)](4-)-H(2)O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H(2)Pc, and [CuPc(SO(3))(4)](4-) in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu(2+) cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO(3)(-) anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.

Assessment of Orbital-Optimized MP2.5 for Thermochemistry and Kinetics: Dramatic Failures of Standard Perturbation Theory Approaches for Aromatic Bond Dissociation Energies and Barrier Heights of Radical Reactions.

PubMed

Soydaş, Emine; Bozkaya, Uğur

2015-04-14

An assessment of orbital-optimized MP2.5 (OMP2.5) [ Bozkaya, U.; Sherrill, C. D. J. Chem. Phys. 2014, 141, 204105 ] for thermochemistry and kinetics is presented. The OMP2.5 method is applied to closed- and open-shell reaction energies, barrier heights, and aromatic bond dissociation energies. The performance of OMP2.5 is compared with that of the MP2, OMP2, MP2.5, MP3, OMP3, CCSD, and CCSD(T) methods. For most of the test sets, the OMP2.5 method performs better than MP2.5 and CCSD, and provides accurate results. For barrier heights of radical reactions and aromatic bond dissociation energies OMP2.5-MP2.5, OMP2-MP2, and OMP3-MP3 differences become obvious. Especially, for aromatic bond dissociation energies, standard perturbation theory (MP) approaches dramatically fail, providing mean absolute errors (MAEs) of 22.5 (MP2), 17.7 (MP2.5), and 12.8 (MP3) kcal mol(-1), while the MAE values of the orbital-optimized counterparts are 2.7, 2.4, and 2.4 kcal mol(-1), respectively. Hence, there are 5-8-folds reductions in errors when optimized orbitals are employed. Our results demonstrate that standard MP approaches dramatically fail when the reference wave function suffers from the spin-contamination problem. On the other hand, the OMP2.5 method can reduce spin-contamination in the unrestricted Hartree-Fock (UHF) initial guess orbitals. For overall evaluation, we conclude that the OMP2.5 method is very helpful not only for challenging open-shell systems and transition-states but also for closed-shell molecules. Hence, one may prefer OMP2.5 over MP2.5 and CCSD as an O(N(6)) method, where N is the number of basis functions, for thermochemistry and kinetics. The cost of the OMP2.5 method is comparable with that of CCSD for energy computations. However, for analytic gradient computations, the OMP2.5 method is only half as expensive as CCSD.

Isotope effect in heavy/light water suspensions of optically active gold nanoparticles

NASA Astrophysics Data System (ADS)

Kutsenko, V. Y.; Artykulnyi, O. P.; Petrenko, V. I.; Avdeev, M. V.; Marchenko, O. A.; Bulavin, L. A.; Snegir, S. V.

2018-04-01

Aqueous suspensions of optically active gold nanoparticles coated with trisodium citrate were synthesized in light (H2O) water and mixture of light and heavy (H2O/D2O) water using the modified Turkevich protocol. The objective of the paper was to verify sensitivity of neutron scattering methods (in particular, neutron reflectometry) to the potential isotope H/D substitution in the stabilizing organic shell around particles in colloidal solutions. First, the isotope effect was studied with respect to the changes in the structural properties of metal particles (size, shape, crystalline morphology) in solutions by electron microscopy including high-resolution transmission electron microscopy from dried systems. The structural factors determining the variation in the adsorption spectra in addition to the change in the optical properties of surrounding medium were discussed. Then, neutron reflectometry was applied to the layered nanoparticles anchored on a silicon wafer via 3-aminopropyltriethoxysilane molecules to reveal the presence of deuterated water molecules in the shell presumably formed by citrate molecules around the metallic core.

Water dynamics in protein hydration shells: the molecular origins of the dynamical perturbation.

PubMed

Fogarty, Aoife C; Laage, Damien

2014-07-17

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra.

Water Dynamics in Protein Hydration Shells: The Molecular Origins of the Dynamical Perturbation

PubMed Central

2014-01-01

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra. PMID:24479585

Nuclear quantum effects in water exchange around lithium and fluoride ions

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

Wilkins, David M.; Manolopoulos, David E.; Dang, Liem X.

2015-02-14

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain reasonably good agreement with experimental data for solutions of lithium by augmenting the Coulombic interactions between the ion and the water molecules with a standard Lennard-Jones ion-oxygen potential, the same is not true for solutions of fluoride, for which we find that a potential with a softer repulsive wall gives much better agreement. A small degree of destabilization of the first hydration shell ismore » found in quantum simulations of both ions when compared with classical simulations, with the shell becoming less sharply defined and the mean residence time of the water molecules in the shell decreasing. In line with these modest differences, we find that the mechanisms of the exchange processes are unaffected by quantization, so a classical description of these reactions gives qualitatively correct and quantitatively reasonable results. We also find that the quantum effects in solutions of lithium are larger than in solutions of fluoride. This is partly due to the stronger interaction of lithium with water molecules, partly due to the lighter mass of lithium and partly due to competing quantum effects in the hydration of fluoride, which are absent in the hydration of lithium.« less

Dissecting the THz spectrum of liquid water from first principles via correlations in time and space.

PubMed

Heyden, Matthias; Sun, Jian; Funkner, Stefan; Mathias, Gerald; Forbert, Harald; Havenith, Martina; Marx, Dominik

2010-07-06

Solvation of molecules in water is at the heart of a myriad of molecular phenomena and of crucial importance to understanding such diverse issues as chemical reactivity or biomolecular function. Complementing well-established approaches, it has been shown that laser spectroscopy in the THz frequency domain offers new insights into hydration from small solutes to proteins. Upon introducing spatially-resolved analyses of the absorption cross section by simulations, the sensitivity of THz spectroscopy is traced back to characteristic distance-dependent modulations of absorption intensities for bulk water. The prominent peak at approximately 200 cm(-1) is dominated by first-shell dynamics, whereas a concerted motion involving the second solvation shell contributes most significantly to the absorption at about 80 cm(-1) approximately 2.4 THz. The latter can be understood in terms of an umbrella-like motion of two hydrogen-bonded tetrahedra along the connecting hydrogen bond axis. Thus, a modification of the hydrogen bond network, e.g., due to the presence of a solute, is expected to affect vibrational motion and THz absorption intensity at least on a length scale that corresponds to two layers of solvating water molecules. This result provides a molecular mechanism explaining the experimentally determined sensitivity of absorption changes in the THz domain in terms of distinct, solute-induced dynamical properties in solvation shells of (bio)molecules--even in the absence of well-defined resonances.

Vibronic Transitions in the X-Sr Series (X=Li, Na, K, Rb): on the Accuracy of Nuclear Wavefunctions Derived from Quantum Chemistry

NASA Astrophysics Data System (ADS)

Meyer, Ralf; Pototschnig, Johann V.; Hauser, Andreas W.; Ernst, Wolfgang E.

2016-06-01

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. The preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. On the theoretical side, highly accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. Particularly problematic is the correct description of potential features at large intermolecular distances. Franck-Condon overlap integrals for nuclear wavefunctions in barely bound vibrational states are extremely sensitive to inaccuracies of the potential at long range. In this study, we compare the predictions of common, wavefunction-based ab initio techniques for a known de-excitation mechanism in alkali-alkaline earth dimers. It is the aim to analyze the predictive power of these methods for a preliminary evaluation of potential cooling mechanisms in heteronuclear open shell systems which offer the experimentalist an electric as well as a magnetic handle for manipulation. The series of X-Sr molecules, with X = Li, Na, K and Rb, has been chosen for a direct comparison. Quantum degenerate mixtures of Rb and Sr have already been produced, making this combination very promising for the production of ultracold molecules. B. Pasquiou, A. Bayerle, S. M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, and F. Schreck, Phys. Rev. A, 2013, 88, 023601

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

Chatterjee, Anupam; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076; Higham, Jonathan

A range of methods are presented to calculate a solute’s hydration shell from computer simulations of dilute solutions of monatomic ions and noble gas atoms. The methods are designed to be parameter-free and instantaneous so as to make them more general, accurate, and consequently applicable to disordered systems. One method is a modified nearest-neighbor method, another considers solute-water Lennard-Jones overlap followed by hydrogen-bond rearrangement, while three methods compare various combinations of water-solute and water-water forces. The methods are tested on a series of monatomic ions and solutes and compared with the values from cutoffs in the radial distribution function, themore » nearest-neighbor distribution functions, and the strongest-acceptor hydrogen bond definition for anions. The Lennard-Jones overlap method and one of the force-comparison methods are found to give a hydration shell for cations which is in reasonable agreement with that using a cutoff in the radial distribution function. Further modifications would be required, though, to make them capture the neighboring water molecules of noble-gas solutes if these weakly interacting molecules are considered to constitute the hydration shell.« less

Solvation of Na^+ in water from first-principles molecular dynamics

NASA Astrophysics Data System (ADS)

White, J. A.; Schwegler, E.; Galli, G.; Gygi, F.

2000-03-01

We have carried out ab initio molecular dynamics (MD) simulations of the Na^+ ion in water with an MD cell containing a single alkali ion and 53 water molecules. The electron-electron and electron-ion interactions were modeled by density functional theory with a generalized gradient approximation for the exchange-correlation functional. The computed radial distribution functions, coordination numbers, and angular distributions are consistent with available experimental data. The first solvation shell contains 5.2±0.6 water molecules, with some waters occasionally exchanging with those of the second shell. The computed Na^+ hydration number is larger than that from calculations for water clusters surrounding an Na^+ ion, but is consistent with that derived from x-ray measurements. Our results also indicate that the first hydration shell is better defined for Na^+ than for K^+ [1], as indicated by the first minimum in the Na-O pair distribution function. [1] L.M. Ramaniah, M. Bernasconi, and M. Parrinello, J. Chem. Phys. 111, 1587 (1999). This work was performed for DOE under contract W-7405-ENG-48.

ZnO/ZnSxSe1-x core/shell nanowire arrays as photoelectrodes with efficient visible light absorption

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Zhan, Xueying; Wang, Yajun; Safdar, Muhammad; Niu, Mutong; Zhang, Jinping; Huang, Ying; He, Jun

2012-08-01

ZnO/ZnSxSe1-x core/shell nanowires have been synthesized on n+-type silicon substrate via a two-step chemical vapor deposition method. Transmission electron microscopy reveals that ZnSxSe1-x can be deposited on the entire surface of ZnO nanowire, forming coaxial heterojunction along ZnO nanowire with very smooth shell surface and high shell thickness uniformity. The photoelectrode after deposition of the ternary alloy shell significantly improves visible light absorption efficiency. Electrochemical impedance spectroscopy results explicitly indicate that the introduction of ZnSxSe1-x shell to ZnO nanowires effectively improves the photogenerated charge separation process. Our finding opens up an efficient means for achieving high efficient energy conversion devices.

Conformation and dynamics of the ligand shell of a water-soluble Au102 nanoparticle.

PubMed

Salorinne, Kirsi; Malola, Sami; Wong, O Andrea; Rithner, Christopher D; Chen, Xi; Ackerson, Christopher J; Häkkinen, Hannu

2016-01-21

Inorganic nanoparticles, stabilized by a passivating layer of organic molecules, form a versatile class of nanostructured materials with potential applications in material chemistry, nanoscale physics, nanomedicine and structural biology. While the structure of the nanoparticle core is often known to atomic precision, gaining precise structural and dynamical information on the organic layer poses a major challenge. Here we report a full assignment of (1)H and (13)C NMR shifts to all ligands of a water-soluble, atomically precise, 102-atom gold nanoparticle stabilized by 44 para-mercaptobenzoic acid ligands in solution, by using a combination of multidimensional NMR methods, density functional theory calculations and molecular dynamics simulations. Molecular dynamics simulations augment the data by giving information about the ligand disorder and visualization of possible distinct ligand conformations of the most dynamic ligands. The method demonstrated here opens a way to controllable strategies for functionalization of ligated nanoparticles for applications.

Conformation and dynamics of the ligand shell of a water-soluble Au102 nanoparticle

PubMed Central

Salorinne, Kirsi; Malola, Sami; Wong, O. Andrea; Rithner, Christopher D.; Chen, Xi; Ackerson, Christopher J.; Häkkinen, Hannu

2016-01-01

Inorganic nanoparticles, stabilized by a passivating layer of organic molecules, form a versatile class of nanostructured materials with potential applications in material chemistry, nanoscale physics, nanomedicine and structural biology. While the structure of the nanoparticle core is often known to atomic precision, gaining precise structural and dynamical information on the organic layer poses a major challenge. Here we report a full assignment of 1H and 13C NMR shifts to all ligands of a water-soluble, atomically precise, 102-atom gold nanoparticle stabilized by 44 para-mercaptobenzoic acid ligands in solution, by using a combination of multidimensional NMR methods, density functional theory calculations and molecular dynamics simulations. Molecular dynamics simulations augment the data by giving information about the ligand disorder and visualization of possible distinct ligand conformations of the most dynamic ligands. The method demonstrated here opens a way to controllable strategies for functionalization of ligated nanoparticles for applications. PMID:26791253

Two-state protein model with water interactions: Influence of temperature on the intrinsic viscosity of myoglobin

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

Bakk, Audun

2001-06-01

We describe a single-domain protein as a two-state system with water interactions. Around the unfolded apolar parts of the protein we incorporate the hydration effect by introducing hydrogen bonds between the water molecules in order to mimic the {open_quotes}icelike{close_quotes} shell structure. Intrinsic viscosity, proportional to the effective hydrodynamic volume, for sperm whale metmyoglobin is assigned from experimental data in the folded and in the denaturated state. By weighing statistically the two states against the degree of folding, we express the total intrinsic viscosity. The temperature dependence of the intrinsic viscosity, for different chemical potentials, is in good correspondence with experimentalmore » data [P. L. Privalov , J. Mol. Biol. >190, 487 (1986)]. Cold and warm unfolding, common to small globular proteins, is also a result of the model.« less

Random-Phase Approximation Methods

NASA Astrophysics Data System (ADS)

Chen, Guo P.; Voora, Vamsee K.; Agee, Matthew M.; Balasubramani, Sree Ganesh; Furche, Filipp

2017-05-01

Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical picture of screening and simple diagrammatic analysis. A new decomposition of the RPA correlation energy into plasmonic modes leads to an appealing visualization of electron correlation in terms of charge density fluctuations. Recent developments in the areas of beyond-RPA methods, RPA correlation potentials, and efficient algorithms for RPA energy and property calculations are reviewed. The ability of RPA to approximately capture static correlation in molecules is quantified by an analysis of RPA natural occupation numbers. We illustrate the use of RPA methods in applications to small-gap systems such as open-shell d- and f-element compounds, radicals, and weakly bound complexes, where semilocal density functional results exhibit strong functional dependence.

Adsorbates in a Box: Titration of Substrate Electronic States

NASA Astrophysics Data System (ADS)

Cheng, Zhihai; Wyrick, Jonathan; Luo, Miaomiao; Sun, Dezheng; Kim, Daeho; Zhu, Yeming; Lu, Wenhao; Kim, Kwangmoo; Einstein, T. L.; Bartels, Ludwig

2010-08-01

Nanoscale confinement of adsorbed CO molecules in an anthraquinone network on Cu(111) with a pore size of ≈4nm arranges the CO molecules in a shell structure that coincides with the distribution of substrate confined electronic states. Molecules occupy the states approximately in the sequence of rising electron energy. Despite the sixfold symmetry of the pore boundary itself, the adsorbate distribution adopts the threefold symmetry of the network-substrate system, highlighting the importance of the substrate even for such quasi-free-electron systems.

Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

PubMed Central

Wang, Xu; Le, Anh-Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

2016-01-01

We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. A simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method. PMID:27025410

Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

NASA Astrophysics Data System (ADS)

Wang, Xu; Le, Anh-Thu; Yu, Chao; Lucchese, R. R.; Lin, C. D.

2016-03-01

We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. A simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method.

The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation

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

Skinner, L. B.; Mineral Physics Institute, Stony Brook University, Stony Brook, New York, New York 11794-2100; Galib, M.

2016-04-07

X-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å{sup 3}. The measurements were conducted at a spatial resolution corresponding to Q{sub max} = 16 Å{sup −1}. The method of data analysis and measurement in this study follows the earlier benchmark results reported for water under ambient conditions having a density of 0.0333 molecules per Å{sup 3} and Q{sub max} = 20 Å{sup −1} [J. Chem. Phys. 138, 074506 (2013)] and at 70 °C having a density of 0.0327 molecules per Å{sup 3} and Q{sub max} = 20more » Å{sup −1} [J. Chem. Phys. 141, 214507 (2014)]. The structure of water is very different at these three different T and P state points and thus they provide the basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3 and 3 Å are nearly unchanged: the peak position, shape, and coordination number are nearly identical to their values under ambient conditions. However, in the region above 3 Å, large structural changes occur with the collapse of the well-defined 2nd shell and shifting of higher shells to shorter distances. The measured structure is compared to simulated structure using intermolecular potentials described by both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005, MB-pol, and mW). The DFT-based, revPBE-D3, method and the many-body empirical potential model, MB-pol, provide the best overall representation of the ambient, high-temperature, and high-pressure data. The revPBE-D3, MB-pol, and the TIP4P/2005 models capture the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which partially encroaches the 1st shell at ambient pressure, is pushed further into the local tetrahedral arrangement at higher pressures by the more distant molecules filling the void space in the network between the 1st and 2nd shells.« less

In-medium similarity renormalization group for closed and open-shell nuclei

NASA Astrophysics Data System (ADS)

Hergert, H.

2017-02-01

We present a pedagogical introduction to the in-medium similarity renormalization group (IMSRG) framework for ab initio calculations of nuclei. The IMSRG performs continuous unitary transformations of the nuclear many-body Hamiltonian in second-quantized form, which can be implemented with polynomial computational effort. Through suitably chosen generators, it is possible to extract eigenvalues of the Hamiltonian in a given nucleus, or drive the Hamiltonian matrix in configuration space to specific structures, e.g., band- or block-diagonal form. Exploiting this flexibility, we describe two complementary approaches for the description of closed- and open-shell nuclei: the first is the multireference IMSRG (MR-IMSRG), which is designed for the efficient calculation of nuclear ground-state properties. The second is the derivation of non-empirical valence-space interactions that can be used as input for nuclear shell model (i.e., configuration interaction (CI)) calculations. This IMSRG+shell model approach provides immediate access to excitation spectra, transitions, etc, but is limited in applicability by the factorial cost of the CI calculations. We review applications of the MR-IMSRG and IMSRG+shell model approaches to the calculation of ground-state properties for the oxygen, calcium, and nickel isotopic chains or the spectroscopy of nuclei in the lower sd shell, respectively, and present selected new results, e.g., for the ground- and excited state properties of neon isotopes.

Properties of Kilonovae from Dynamical and Post-merger Ejecta of Neutron Star Mergers

NASA Astrophysics Data System (ADS)

Tanaka, Masaomi; Kato, Daiji; Gaigalas, Gediminas; Rynkun, Pavel; Radžiūtė, Laima; Wanajo, Shinya; Sekiguchi, Yuichiro; Nakamura, Nobuyuki; Tanuma, Hajime; Murakami, Izumi; Sakaue, Hiroyuki A.

2018-01-01

Ejected material from neutron star mergers gives rise to electromagnetic emission powered by radioactive decays of r-process nuclei, the so-called kilonova or macronova. While properties of the emission are largely affected by opacities in the ejected material, available atomic data for r-process elements are still limited. We perform atomic structure calculations for r-process elements: Se (Z = 34), Ru (Z = 44), Te (Z = 52), Ba (Z = 56), Nd (Z = 60), and Er (Z = 68). We confirm that the opacities from bound–bound transitions of open f-shell, lanthanide elements (Nd and Er) are higher than those of the other elements over a wide wavelength range. The opacities of open s-shell (Ba), p-shell (Se and Te), and d-shell (Ru) elements are lower than those of open f-shell elements, and their transitions are concentrated in the ultraviolet and optical wavelengths. We show that the optical brightness can be different by > 2 mag depending on the element abundances in the ejecta such that post-merger, lanthanide-free ejecta produce brighter and bluer optical emission. Such blue emission from post-merger ejecta can be observed from the polar directions if the mass of the preceding dynamical ejecta in these regions is small. For the ejecta mass of 0.01 {M}ȯ , observed magnitudes of the blue emission will reach 21.0 mag (100 Mpc) and 22.5 mag (200 Mpc) in the g and r bands within a few days after the merger, which are detectable with 1 m or 2 m class telescopes.

Expanding relativistic shells and gamma-ray burst temporal structure

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

Fenimore, E.E.; Madras, C.D.; Nayakshin, S.

1996-12-01

Many models of gamma-ray bursts (GRBs) involve a shell expanding at extreme relativistic speeds. The shell of material expands in a photon-quiet phase for a period {ital t}{sub 0} and then becomes gamma-ray active, perhaps due to inhomogeneities in the interstellar medium or the generation of shocks. Based on kinematics, we relate the envelope of the emission of the event to the characteristics of the photon-quiet and photon-active phases. We initially assume local spherical symmetry wherein, on average, the same conditions prevail over the shell`s surface within angles the order of {Gamma}{sup {minus}1}, where {Gamma} is the Lorentz factor formore » the bulk motion. The contribution of the curvature to the temporal structure is comparable to the contribution from the overall expansion. As a result, GRB time histories from a shell should have an envelope similar to {open_quotes}FRED{close_quotes} (fast rise, exponential decay) events in which the rise time is related to the duration of the photon-active phase and the fall time is related to the duration of the photon-quiet phase. This result depends only on local spherical symmetry and, since most GRBs do not have such envelopes, we introduce the {open_quotes}shell symmetry{close_quotes} problem: the observed time history envelopes of most GRBs do not agree with that expected for a relativistic expanding shell. Although FREDs have the signature of a relativistic shell, they may not be due to a single shell, as required by some cosmological models. Some FREDs have precursors in which the peaks are separated by more than the expansion time required to explain FRED shape. Such a burst is most likely explained by a central engine; that is, the separation of the multiple peaks occurs because the central site produced multiple releases of energy on timescales comparable to the duration of the event. (Abstract Truncated)« less

Large-Scale Trade in Legally Protected Marine Mollusc Shells from Java and Bali, Indonesia.

PubMed

Nijman, Vincent; Spaan, Denise; Nekaris, K Anne-Isola

2015-01-01

Tropical marine molluscs are traded globally. Larger species with slow life histories are under threat from over-exploitation. We report on the trade in protected marine mollusc shells in and from Java and Bali, Indonesia. Since 1987 twelve species of marine molluscs are protected under Indonesian law to shield them from overexploitation. Despite this protection they are traded openly in large volumes. We collected data on species composition, origins, volumes and prices at two large open markets (2013), collected data from wholesale traders (2013), and compiled seizure data by the Indonesian authorities (2008-2013). All twelve protected species were observed in trade. Smaller species were traded for 32,000 shells valued at USD500,000), chambered nautilus (Nautilus pompilius) (>3,000 shells, USD60,000) and giant clams (Tridacna spp.) (>2,000 shells, USD45,000) were traded in largest volumes. Two-thirds of this trade was destined for international markets, including in the USA and Asia-Pacific region. We demonstrated that the trade in protected marine mollusc shells in Indonesia is not controlled nor monitored, that it involves large volumes, and that networks of shell collectors, traders, middlemen and exporters span the globe. This impedes protection of these species on the ground and calls into question the effectiveness of protected species management in Indonesia; solutions are unlikely to be found only in Indonesia and must involve the cooperation of importing countries.

Atomistic simulations of cation hydration in sodium and calcium montmorillonite nanopores

NASA Astrophysics Data System (ADS)

Yang, Guomin; Neretnieks, Ivars; Holmboe, Michael

2017-08-01

During the last four decades, numerous studies have been directed to the swelling smectite-rich clays in the context of high-level radioactive waste applications and waste-liners for contaminated sites. The swelling properties of clay mineral particles arise due to hydration of the interlayer cations and the diffuse double layers formed near the negatively charged montmorillonite (MMT) surfaces. To accurately study the cation hydration in the interlayer nanopores of MMT, solvent-solute and solvent-clay surface interactions (i.e., the solvation effects and the shape effects) on the atomic level should be taken into account, in contrast to many recent electric double layer based methodologies using continuum models. Therefore, in this research we employed fully atomistic simulations using classical molecular dynamics (MD) simulations, the software package GROMACS along with the CLAYFF forcefield and the SPC/E water model. We present the ion distributions and the deformation of the hydrated coordination structures, i.e., the hydration shells of Na+ and Ca2+ in the interlayer, respectively, for MMT in the first-layer, the second-layer, the third-layer, the fourth-layer, and the fifth-layer (1W, 2W, 3W, 4W, and 5W) hydrate states. Our MD simulations show that Na+ in Na-MMT nanopores have an affinity to the ditrigonal cavities of the clay layers and form transient inner-sphere complexes at about 3.8 Å from clay midplane at water contents less than the 5W hydration state. However, these phenomena are not observed in Ca-MMT regardless of swelling states. For Na-MMT, each Na+ is coordinated to four water molecules and one oxygen atom of the clay basal-plane in the first hydration shell at the 1W hydration state, and with five to six water molecules in the first hydration shell within a radius of 3.1 Å at all higher water contents. In Ca-MMT, however each Ca2+ is coordinated to approximately seven water molecules in the first hydration shell at the 1W hydration state and about eight water molecules in the first hydration shell within a radius of 3.3 Å at all higher hydration states. Moreover, the MD results show that the complete hydration shells are nearly spherical with an orthogonal coordination sphere. They could only be formed when the basal spacing d001 ≥ 18.7 Å, i.e., approximately, the interlayer separation h ≥ 10 Å. Comparison between DFT and MD simulations shows that DFT failed to reproduce the outer-sphere complexes in the Stern-layer (within ˜5.0 Å from the clay basal-plane), observed in the MD simulations.

DNA bases ring-expanded with a cyclopentadiene free radical: a theoretical investigation of building blocks with diradical character.

PubMed

Zhao, Peiwen; Bu, Yuxiang

2016-01-14

In this work, we computationally design radical nucleobases which possess improved electronic properties, especially diradical properties through introducing a cyclopentadiene radical. We predict that the detailed electromagnetic features of base assemblies are based on the orientation of the extra five-membered cyclopentadiene ring. Broken symmetry DFT calculations take into account the relevant structures and properties. Our results reveal that both the radicalized DNA bases and the base pairs formed when they combine with their counterparts remain stable and display larger spin delocalization. The mode of embedding the cyclopentadiene free radical in the structures has some influence on the degree of π-conjugation, which results in various diradical characteristics. Single-layered radical base pairs all have an open-shell singlet ground state, but the energy difference between singlet and triplet is not significant. For two-layered radical base pairs, the situation is more complex. All of them have an open-shell state as their ground state, including an open-shell singlet state and an open-shell triplet state. That is, the majority of radical base pairs possess anti-ferromagnetic or ferromagnetic characteristics. We present here a more in-depth discussion and analyses to study the magnetic characteristics of radical bases and base pairs. As an important factor, two-layered radical base pairs also have been carefully analyzed. We hope that all the measurements and results presented here will stimulate further detailed insights into the related mechanisms in modified DNA bases and the design of better ring-expanded DNA magnetic materials.

Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell.

PubMed

Bodo, Enrico

2015-09-03

By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).

Analytic energy gradients in combined second order Møller-Plesset perturbation theory and conductorlike polarizable continuum model calculation.

PubMed

Si, Dejun; Li, Hui

2011-10-14

The analytic energy gradients in combined second order Møller-Plesset perturbation theory and conductorlike polarizable continuum model calculations are derived and implemented for spin-restricted closed shell (RMP2), Z-averaged spin-restricted open shell (ZAPT2), and spin-unrestricted open shell (UMP2) cases. Using these methods, the geometries of the S(0) ground state and the T(1) state of three nucleobase pairs (guanine-cytosine, adenine-thymine, and adenine-uracil) in the gas phase and aqueous solution phase are optimized. It is found that in both the gas phase and the aqueous solution phase the hydrogen bonds in the T(1) state pairs are weakened by ~1 kcal/mol as compared to those in the S(0) state pairs. © 2011 American Institute of Physics

Accurate structure, thermodynamics and spectroscopy of medium-sized radicals by hybrid Coupled Cluster/Density Functional Theory approaches: the case of phenyl radical

PubMed Central

Barone, Vincenzo; Biczysko, Malgorzata; Bloino, Julien; Egidi, Franco; Puzzarini, Cristina

2015-01-01

The CCSD(T) model coupled with extrapolation to the complete basis-set limit and additive approaches represents the “golden standard” for the structural and spectroscopic characterization of building blocks of biomolecules and nanosystems. However, when open-shell systems are considered, additional problems related to both specific computational difficulties and the need of obtaining spin-dependent properties appear. In this contribution, we present a comprehensive study of the molecular structure and spectroscopic (IR, Raman, EPR) properties of the phenyl radical with the aim of validating an accurate computational protocol able to deal with conjugated open-shell species. We succeeded in obtaining reliable and accurate results, thus confirming and, partly, extending the available experimental data. The main issue to be pointed out is the need of going beyond the CCSD(T) level by including a full treatment of triple excitations in order to fulfil the accuracy requirements. On the other hand, the reliability of density functional theory in properly treating open-shell systems has been further confirmed. PMID:23802956

Processes of energy deposition by heavy-particle and electron impact. Final progress report

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

Salop, A.; Smith, F.T.

1978-04-18

Progress is reported in three areas of reasearch during the present period: K-shell ionization in high energy collisions of heavy ions with light target atoms using the sudden (Magnus) approximation, K-L level matching phenomena associated with K-shell vacancy production in heavy-ion collisions, and studies of low energy collisions of electrons with molecules using semi-classical perturbation theory. A brief discussion of each of these activities is given.

Interruption of Hydrogen Bonding Networks of Water in Carbon Nanotubes Due to Strong Hydration Shell Formation.

PubMed

Oya, Yoshifumi; Hata, Kenji; Ohba, Tomonori

2017-10-24

We present the structures of NaCl aqueous solution in carbon nanotubes with diameters of 1, 2, and 3 nm based on an analysis performed using X-ray diffraction and canonical ensemble Monte Carlo simulations. Anomalously longer nearest-neighbor distances were observed in the electrolyte for the 1-nm-diameter carbon nanotubes; in contrast, in the 2 and 3 nm carbon nanotubes, the nearest-neighbor distances were shorter than those in the bulk electrolyte. We also observed similar properties for water in carbon nanotubes, which was expected because the main component of the electrolyte was water. However, the nearest-neighbor distances of the electrolyte were longer than those of water in all of the carbon nanotubes; the difference was especially pronounced in the 2-nm-diameter carbon nanotubes. Thus, small numbers of ions affected the entire structure of the electrolyte in the nanopores of the carbon nanotubes. The formation of strong hydration shells between ions and water molecules considerably interrupted the hydrogen bonding between water molecules in the nanopores of the carbon nanotubes. The hydration shell had a diameter of approximately 1 nm, and hydration shells were thus adopted for the nanopores of the 2-nm-diameter carbon nanotubes, providing an explanation for the large difference in the nearest-neighbor distances between the electrolyte and water in these nanopores.

Organic-dye-coupled magnetic nanoparticles encaged inside thermoresponsive PNIPAM Microcapsules.

PubMed

Guo, Jia; Yang, Wuli; Deng, Yonghui; Wang, Changchun; Fu, Shoukuan

2005-07-01

We present a new approach for the fabrication of thermoresponsive polymer microcapsules with mobile magnetic cores that undergo a volume phase-transition upon changing the temperature and are collected under an external magnetic field. We have prepared organic/inorganic composite microspheres with a well-defined core-shell structure that are composed of a crosslinked poly(N-isopropylacrylamide) (PNIPAM) shell and silica cores dotted centrally by magnetite nanoparticles. Since the infiltration of template-decomposed products is dependent on the permeability of PNIPAM shells triggered by changes of exterior temperature, the silica layer sandwiched between the magnetic core and the PNIPAM shell was quantitatively removed to generate PNIPAM microcapsules with mobile magnetic cores by treatment with aqueous NaOH solution. For development of the desired multifunctional microcapsules, modification of the unetched silica surface interiors can be realized by treatment with a silane coupling agent containing functional groups that can easily bind to catalysts, enzymes, or labeling molecules. Herein, fluorescein isothiocyanate (FITC), which is a common organic dye, is attached to the insides of the mobile magnetic cores to give PNIPAM microcapsules with FITC-labeled magnetic cores. In this system, it can be expected that an extension of the functionalization of the cavity properties of smart polymer microcapsules is to immobilize other target molecules onto the mobile cores in order to introduce other desired functions in the hollow cage.

Heat resistant protective hand covering

NASA Technical Reports Server (NTRS)

Sidman, K. R.; Arons, I. J. (Inventor)

1984-01-01

The heat resistant, protective glove is made up of first and second shell sections which define a palm side and a backside, respectively. The first shell section is made of a twill wave fabric of a temperature-resistant aromatic polyamide fiber. The second shell section is made of a knitted fabric of a temperature-resistant aromatic polyamide fiber. The first and second shell sections are secured to one another, e.g., by sewing, to provide the desired glove configuration and an opening for insertion of the wearer's hand. The protective glove also includes a first liner section which is secured to and overlies the inner surface of the first shell section and is made of a felt fabric of a temperature-resistant aromatic polyamide fiber and has a flame resistant, elastomenic coating on the surface facing and overlying the inner surface of the first shell section.

Discovery of Molecular Gas Shells around the Unusual Galaxy Centaurus A

NASA Astrophysics Data System (ADS)

2000-03-01

Recent observations by an international team of astronomers [1] with the 15-metre Swedish-ESO Submillimetre Telescope at the La Silla observatory (Chile) have shown that the unusual, nearby galaxy Centaurus A is surrounded by shells in which carbon monoxide molecules are present. These new exciting results are the first of their kind. In addition to the intrinsic scientific value of this discovery, it also provides an instructive example of what will become possible for more distant galaxies with the projected Atacama Large Millimeter Array (ALMA) , now in the planning phase. Ellipticals and spirals Galaxies come in different shapes. Some of these take the form of more or less perfect spirals, some have the form of ellipsoids and still others have an irregular appearance. One of the major differences between elliptical and spiral galaxies is that the former do not possess extensive gaseous discs in which young stars can be formed. This is despite the fact that most elliptical galaxies are probably formed by the merger of two or more spiral galaxies. However, during such a process most of the gas in the spirals is either quickly turned into stars by massive bursts of star formation or is completely lost into the surrounding space. Shells around elliptical galaxies Most galaxies are members of groups. Once they have been formed, massive elliptical galaxies in these often behave like "cannibals" by swallowing one or more smaller companion galaxies. Some vestiges of such an event may remain visible for a certain time after the merger, normally in the form of weak structures in the otherwise smooth light distribution over the elliptical galaxy. These structures resemble the ripples or waves that develop on the water surface when you throw a small stone into a calm pond. While long-exposure photos show them as faint "rings" around the galaxy, they are in fact the projected images of three-dimensional structures and are often referred to as shells . By means of photometric and spectrographic studies of their light, it has been known since the early 1980's that such shells are made up of stars. It appears that they are quite common - about half of the nearby large elliptical galaxies have been found to be surrounded by stellar shells. More recently, in 1994, atomic hydrogen gas was discovered to be associated with some of the stellar shells. This discovery was a bit of a surprise, because the current theory predicts that when two galaxies merge, their gas and stars will behave very differently. While the individual stars hardly ever hit each other, the interstellar gas clouds collide violently. They will lose all their energy and the gas will fall towards the common centre where it is soon consumed in vigorous bursts of star formation. Why would there then be hydrogen gas in the outer shells of some elliptical galaxies? A possible origin of gaseous shells The astronomer team, headed by Vassilis Charmandaris [1] decided to look into this serious discrepancy between theory and observations. They believed that a possible explanation might be that this diffuse atomic gas is located, not in vast, very dilute clouds, but rather in smaller, much denser molecular clouds , such as these are known in our own galaxy, the Milky Way. Due to their relative compactness (more than 1000 molecules/cm 3 , i.e,. at least 100 times more than that of larger diffuse clouds), molecular clouds would behave more like the stars during the galaxy collision event. Indeed, realistic calculations showed that the dynamical behavior of such dense clouds would be intermediate between the stars and the diffuse hydrogen gas. Thus, while most of the gas would still end up in the centre of the remaining galaxy after a merger, a larger fraction of it would be able to survive at large distances from the nucleus. This would then be the origin of the observed hydrogen shells. During the merger, gas that originates from regions in the outskirts of the "cannibalized" galaxy - and farther out than most of the stars - would be liberated earlier than the stars. As a consequence, one would also expect to observe a certain displacement between the gaseous and stellar shells. The SEST observations ESO PR Photo 08a/00 ESO PR Photo 08a/00 [Preview - JPEG: 343 x 400 pix - 188k] [Normal - JPEG: 686 x 800 pix - 560k] [High-Res - JPEG: 2571 x 3000 pix - 4.4M] Caption : ESO PR Photo 08a/00 shows an optical image of the galaxy Centaurus A (from the 1-m ESO Schmidt telescope at La Silla), with the surrounding shells outlined as contours. The image has been enhanced to show the full extent of the galaxy; due to this process, the central dust band is less visible. The stellar shells (see the text) are indicated in yellow; they are otherwise only visible on very deep images. The contours of the observed distribution of atomic hydrogen gas are white. The radio jet from the active centre of Centaurus A is shown in blue. The new SEST observations prove the existence of carbon monoxide (CO) in the S1 and S2 shells (indicated in red). The field measures approx. 32 x 32 arcmin 2. North is up and East is left. A detailed photo of Centaurus A was recently obtained with the FORS2 instrument at VLT KUEYEN, cf. ESO PR Photo 05b/00 ESO PR Photo 08b/00 ESO PR Photo 08b/00 [Preview - JPEG: 247 x 400 pix - 60k] [Normal - JPEG: 493 x 800 pix - 128k] [High-Res - JPEG: 3000 x 1847 pix - 756k] Caption : ESO PR Photo 08b/00 shows the observed CO emission spectra in the S1 and S2 shells. In both cases, two lines from different molecular states were observed that stand out clearly from the sky noise. The abscissa indicates the velocity (i.e., the radio frequency) and the ordinate the temperature (i.e., the intensity). These diagrammes represent approx. 20 and 30 hours of observation, respectively. In order to test this hypothesis, the astronomers decided to look for the possible presence in the shells around some nearby elliptical galaxies of specific gases that are typical of molecular clouds . The observations were carried out with the 15-metre Swedish-ESO Submillimetre Telescope (SEST) at the ESO La Silla Observatory (Chile). This telescope is the only one of its kind in the southern hemisphere and is particularly suited to register emissions from gases that are common in molecular clouds, e.g. those of carbon monoxide (CO) near a wavelength of 3 mm . This search was successful, notably in the case of Centaurus A , a nearby giant elliptical galaxy with strong radio emission and an active nucleus (AGN), cf. ESO PR Photos 05b-c/00. For the first time, carbon monoxide molecules (CO) were found to be present in two of the surrounding shells, cf. PR Photo 08a/00 . These shells are located at a distance of about 50,000 light-years (15 kpc) from the nucleus of the galaxy and, as can be seen on the photo, the regions of the observed molecules appear to be aligned with the radio jet. This important discovery supports the above mentioned hypothesis and thus provides an important clue as to why there can be gas very far from the centre of an elliptical galaxy after a collision/merger. It is therefore likely that a certain fraction of the gas in the "cannibalized" companion galaxy is made up by small and dense molecular clouds. During the collision, they behave similarly to the stars and end up by forming gaseous shells. The fate of the gas in the shells What is then the likely fate of these gaseous shells? They are most certainly gravitationally well bound to the Centaurus A galaxy and cannot escape into the surrounding intergalactic space. But while the thin and diffuse hydrogen gas will probably move towards the galaxy centre fairly quickly, the more clumpy clouds and the molecular gas therein may remain in the outer shells during long periods. Over time though, also this gas will become less prominent, as the clouds slowly disperse. Interesting perspectives The discovery of carbon monoxide in the shells around Centaurus A opens very interesting avenues for future research on the evolution of galaxies. However, observations like these are very challenging. First of all, as there are comparatively small quantities of gas in most galaxy shells, such measurements require large radio telescopes with high-sensitivity receivers, as well as many hours of observation before sufficiently accurate results (i.e., signal-to-noise ratio) are obtained. In the present case, no less than 20 hours were needed to achieve the secure detection of the emission from CO molecules, as displayed in PR Photo 08b/00 . Moreover, the angular resolution on the sky of the single 15-metre SEST dish is only about 44 arcsec (at the wavelengths of the observed CO lines around 3 mm). This makes it virtually impossible to obtain a clear view of the individual shells in distant galaxies with this telescope. On the other hand, in nearby targets such as Centaurus A, the shells extend over a comparatively large sky area and thus require large-scale mapping, a very time-consuming project. The role of ALMA However, exciting possibilities for more detailed studies, also of much more distant galaxies, are opening with the future Atacama Large Millimeter Array (ALMA) . The collecting area of ALMA is about 7000 m 2 , or over 40 times larger than that of SEST. It will also achieve sub-arcsecond angular resolution when its 64 antennas are combined in the interferometric mode. Together, these properties of ALMA will allow much more sensitive and detailed observations of galaxies at larger distances. When compared to earlier observations of CO near the centre of Centaurus A, the present SEST data show that about 10% of the molecular gas is far outside the centre of this galaxy. As a next step, it would be interesting to examine whether this is also true in other elliptical galaxies with gaseous shells. And will it be possible to detect other molecules in these shells? There will certainly be no lack of opportunities for exciting research in this field, especially with the advent of ALMA , some years from now. More information about this project A research article about this project will appear in the European journal Astronomy & Astrophysics (Vol. 356); it is now available on the web at astro-ph/0003175. Note [1] The team consists of Vassilis Charmandaris (DEMIRM, Observatoire de Paris, France and Cornell University, USA), Françoise Combes (DEMIRM, Observatoire de Paris, France) and Thijs van der Hulst (Kapteyn Institute, University of Groningen, The Netherlands). This work was supported by the European Union via a Marie-Curie fellowship. Contact Dr. Vassilis Charmandaris , Cornell University, Astronomy Department, 106 Space Sciences Bldg., Ithaca, NY 14853, USA. Tel.: +1 (607) 255-8774; e-mail: vassilis@astro.cornell.edu ESO PR Photos may be reproduced, if credit is given to the European Southern Observatory.

One-by-one imprinting in two eccentric layers of hollow core-shells: Sequential electroanalysis of anti-HIV drugs.

PubMed

Singh, Kislay; Jaiswal, Swadha; Singh, Richa; Fatma, Sana; Prasad, Bhim Bali

2018-07-15

Double layered one-by-one imprinted hollow core-shells@ pencil graphite electrode was fabricated for sequential sensing of anti-HIV drugs. For this, two eccentric layers were developed on the surface of vinylated silica nanospheres to obtain double layered one-by-one imprinted solid core-shells. This yielded hollow core-shells on treatment with hydrofluoric acid. The modified hollow core-shells (single layered dual imprinted) evolved competitive diffusion of probe/analyte molecules. However, the corresponding double layered one-by-one imprinted hollow core-shells (outer layer imprinted with Zidovudine, and inner layer with Lamivudine) were found relatively better owing to their bilateral diffusions into molecular cavities, without any competition. The entire work is based on differential pulse anodic stripping voltammetry at double layered one-by-one imprinted hollow core-shells. This resulted in indirect detection of electro inactive targets with limits of detection as low as 0.91 and 0.12 (aqueous sample), 0.94 and 0.13 (blood serum), and 0.99 and 0.20 ng mL -1 (pharmaceutics) for lamivudine and zidovudine, respectively in anti-HIV drug combination. Copyright © 2018 Elsevier B.V. All rights reserved.

Evolution of a compound droplet attached to a core-shell nozzle under the action of a strong electric field

NASA Astrophysics Data System (ADS)

Reznik, S. N.; Yarin, A. L.; Zussman, E.; Bercovici, L.

2006-06-01

The shape evolution of small compound droplets at the exit of a core-shell system in the presence of a sufficiently strong electric field is studied both experimentally and theoretically. It is shown that the jetting effect at the tip of the shell nozzle does not necessarily cause entrainment of the core fluid, in which case the co-electrospinning process fails to produce core-shell nanofibers. The remedy lies in extending the core nozzle outside its shell counterpart by about half the radius of the latter. The results also show that the free charges migrate very rapidly from both fluids and their interface to the free surface of the shell. This reflects the fact that most of the prejetting evolution of the droplet can be effectively described in terms of the perfect conductor model, even though the fluids can be characterized as leaky dielectrics. The stress level at the core-shell interface is of the order of 5×103g/(cms2), the relevant value in assessing the viability of viruses, bacteria, DNA molecules, drugs, enzymes, chromophores, and proteins to be encapsulated in nanofibers via co-electrospinning.

A Plasmonic Colloidal Photocatalyst Composed of a Metal-Organic Framework Core and a Gold/Anatase Shell for Visible-Light-Driven Wastewater Purification from Antibiotics and Hydrogen Evolution.

PubMed

Tilgner, Dominic; Kempe, Rhett

2017-03-02

Porous coordination polymers (PCP) or metal- organic frameworks (MOF) are promising materials for the generation of photocatalytically active composite materials. Here, a novel synthesis concept is reported, which permits the formation of PCP/MOF-core-Au/anatase-shell materials. These materials are photocatalysts for wastewater purification and hydrogen generation from water under visible-light illumination. MIL-101 (Cr) is utilized as the core material, which directs the size of the core-shell compound and ensures the overall stability. In addition, its excellent reversible large molecule sorption behavior allows the materials synthesis. The crystalline anatase shell is generated stepwise under mild conditions using titanium(IV) isopropoxide as a precursor. The high degree of control of the vapor phase deposition process permits the precise anatase shell formation. The generation of plasmonic active gold particles on the TiO 2 shell leads to an efficient material for visible-light-driven photocatalysis with a higher activity than gold-decorated P25 (Degussa). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extended fenske-hall calculation of inner-shell binding energies using ( Z + 1)-bazis sets: Sulfur-containing molecules

NASA Astrophysics Data System (ADS)

Zwanziger, Ch.; Zwanziger, H.; Szargan, R.; Reinhold, J.

1981-08-01

It is shown that the S1s and S2p binding energies and their chemical shifts in the molecules H 2S, SO 2, SF 6 and COS obtained with hole-state calculations using an extended Fenske-Hall method are in good agreement with experimental values if mixed ( Z + 1)-basis sets are applied.

Dielectric properties of almond shells in the development of radio frequency and microwave pasteurization

USDA-ARS?s Scientific Manuscript database

To develop pasteurization treatments based on radio frequency (RF) or microwave energy, dielectric properties of almond shells were determined using an open-ended coaxial-probe with an impedance analyzer over a frequency range of 10 to 1800 MHz. Both the dielectric constant and loss factor of almond...

High Level ab initio Predictions of the Energetics of mCO2•(H2O)n (n = 1-3, m = 1-12) Clusters

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

Thanthiriwatte, Sahan; Duke, Jessica R.; Jackson, Virgil E.

Electronic structure calculations at the correlated molecular orbital theory and density functional theory levels have been used to generate a reliable set of clustering energies for up to three water molecules in carbon dioxide clusters up to n = 12. The structures and energetics are dominated by Lewis acid-base interactions with hydrogen bonding interactions playing a lesser energetic role. The actual binding energies are somewhat larger than might be expected. The correlated molecular orbital MP2 method and density functional theory with the ωB97X exchange-correlation functional provide good results for the energetics of the clusters but the B3LYP and ωB97X-D functionalsmore » do not. Seven CO2 molecules form the first solvent shell about a single H2O with four CO2 molecules interacting with the H2O via Lewis acid-base interactions, two CO2 interacting with the H2O by hydrogen bonds, and the seventh CO2 completing the shell. The Lewis acid-base and weak hydrogen bond interactions between the water molecules and the CO2 molecules are strong enough to disrupt the trimer ring configuration for as few as seven CO2 molecules. Calculated 13C NMR chemical shifts for mCO2•(H2O)n show little change with respect to the number of H2O or CO2 molecules in the cluster. The O-H stretching frequencies do exhibit shifts that can provide information about the interactions between water and CO2 molecules.« less

Preparation, process optimization and characterization of core-shell polyurethane/chitosan nanofibers as a potential platform for bioactive scaffolds.

PubMed

Maleknia, Laleh; Dilamian, Mandana; Pilehrood, Mohammad Kazemi; Sadeghi-Aliabadi, Hojjat; Hekmati, Amir Houshang

2018-06-01

In this paper, polyurethane (PU), chitosan (Cs)/polyethylene oxide (PEO), and core-shell PU/Cs nanofibers were produced at the optimal processing conditions using electrospinning technique. Several methods including SEM, TEM, FTIR, XRD, DSC, TGA and image analysis were utilized to characterize these nanofibrous structures. SEM images exhibited that the core-shell PU/Cs nanofibers were spun without any structural imperfections at the optimized processing conditions. TEM image confirmed the PU/Cs core-shell nanofibers were formed apparently. It that seems the inclusion of Cs/PEO to the shell, did not induce the significant variations in the crystallinity in the core-shell nanofibers. DSC analysis showed that the inclusion of Cs/PEO led to the glass temperature of the composition increased significantly compared to those of neat PU nanofibers. The thermal degradation of core-shell PU/Cs was similar to PU nanofibers degradation due to the higher PU concentration compared to other components. It was hypothesized that the core-shell PU/Cs nanofibers can be used as a potential platform for the bioactive scaffolds in tissue engineering. Further biological tests should be conducted to evaluate this platform as a three dimensional scaffold with the capabilities of releasing the bioactive molecules in a sustained manner.

Effects of scallop shell extract on scopolamine-induced memory impairment and MK801-induced locomotor activity.

PubMed

Hasegawa, Yasushi; Inoue, Tatsuro; Kawaminami, Satoshi; Fujita, Miho

2016-07-01

To evaluate the neuroprotective effects of the organic components of scallop shells (scallop shell extract) on memory impairment and locomotor activity induced by scopolamine or 5-methyl-10,11-dihydro-5H-dibenzo (a,d) cyclohepten-5,10-imine (MK801). Effect of the scallop shell extract on memory impairment and locomotor activity was investigated using the Y-maze test, the Morris water maze test, and the open field test. Scallop shell extract significantly reduced scopolamine-induced short-term memory impairment and partially reduced scopolamine-induced spatial memory impairment in the Morris water maze test. Scallop shell extract suppressed scopolamine-induced elevation of acetylcholine esterase activity in the cerebral cortex. Treatment with scallop shell extract reversed the increase in locomotor activity induced by scopolamine. Scallop shell extract also suppressed the increase in locomotor activity induced by MK801. Our results provide initial evidence that scallop shell extract reduces scopolamine-induced memory impairment and suppresses MK-801-induced hyperlocomotion. Copyright © 2016 Hainan Medical College. Production and hosting by Elsevier B.V. All rights reserved.

Neutron Nucleic Acid Crystallography.

PubMed

Chatake, Toshiyuki

2016-01-01

The hydration shells surrounding nucleic acids and hydrogen-bonding networks involving water molecules and nucleic acids are essential interactions for the structural stability and function of nucleic acids. Water molecules in the hydration shells influence various conformations of DNA and RNA by specific hydrogen-bonding networks, which often contribute to the chemical reactivity and molecular recognition of nucleic acids. However, X-ray crystallography could not provide a complete description of structural information with respect to hydrogen bonds. Indeed, X-ray crystallography is a powerful tool for determining the locations of water molecules, i.e., the location of the oxygen atom of H2O; however, it is very difficult to determine the orientation of the water molecules, i.e., the orientation of the two hydrogen atoms of H2O, because X-ray scattering from the hydrogen atom is very small.Neutron crystallography is a specialized tool for determining the positions of hydrogen atoms. Neutrons are not diffracted by electrons, but are diffracted by atomic nuclei; accordingly, neutron scattering lengths of hydrogen and its isotopes are comparable to those of non-hydrogen atoms. Therefore, neutron crystallography can determine both of the locations and orientations of water molecules. This chapter describes the current status of neutron nucleic acid crystallographic research as well as the basic principles of neutron diffraction experiments performed on nucleic acid crystals: materials, crystallization, diffraction experiments, and structure determination.

Monodisperse MnO2@NiCo2O4 core/shell nanospheres with highly opened structures as electrode materials for good-performance supercapacitors

NASA Astrophysics Data System (ADS)

Zhou, You; Ma, Li; Gan, Mengyu; Ye, Menghan; Li, Xiurong; Zhai, Yanfang; Yan, Fabing; Cao, Feifei

2018-06-01

The monodisperse MnO2@NiCo2O4 core/shell nanospheres for good-performance supercapacitors are designed and synthesized by a two-step solution-based method and a simple post annealing process. In the composite, both MnO2 (the "core") and NiCo2O4 (the "shell") are formed by the accumulation of nanoflakes. Thus, nearly all the core/shell nanoflakes are highly opened and accessible to electrolyte, making them give full play to the Faradaic reaction. Our results demonstrate that the composite electrode exhibits desirable pseudocapacitive behaviors with higher specific capacitance (1127.27 F g-1 at a current density of 1 A g-1), better rate capability (81.0% from 1 to 16 A g-1) and superior cycling stability (actually 126.8% capacitance retention after 1000 cycles and only 3.7% loss after 10,000 cycles at 10 A g-1) in 3 M KOH aqueous solution. Moreover, it offers the excellent specific energy density of 26.6 Wh kg-1 at specific power density of 800 W kg-1. The present MnO2@NiCo2O4 core/shell nanospheres with remarkable electrochemical properties are considered as potential electrode materials for the next generation supercapacitors.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

PubMed

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Overcoming computational uncertainties to reveal chemical sensitivity in single molecule conduction calculations.

PubMed

Solomon, Gemma C; Reimers, Jeffrey R; Hush, Noel S

2005-06-08

In the calculation of conduction through single molecule's approximations about the geometry and electronic structure of the system are usually made in order to simplify the problem. Previously [G. C. Solomon, J. R. Reimers, and N. S. Hush, J. Chem. Phys. 121, 6615 (2004)], we have shown that, in calculations employing cluster models for the electrodes, proper treatment of the open-shell nature of the clusters is the most important computational feature required to make the results sensitive to variations in the structural and chemical features of the system. Here, we expand this and establish a general hierarchy of requirements involving treatment of geometrical approximations. These approximations are categorized into two classes: those associated with finite-dimensional methods for representing the semi-infinite electrodes, and those associated with the chemisorption topology. We show that ca. 100 unique atoms are required in order to properly characterize each electrode: using fewer atoms leads to nonsystematic variations in conductivity that can overwhelm the subtler changes. The choice of binding site is shown to be the next most important feature, while some effects that are difficult to control experimentally concerning the orientations at each binding site are actually shown to be insignificant. Verification of this result provides a general test for the precision of computational procedures for molecular conductivity. Predictions concerning the dependence of conduction on substituent and other effects on the central molecule are found to be meaningful only when they exceed the uncertainties of the effects associated with binding-site variation.

Overcoming computational uncertainties to reveal chemical sensitivity in single molecule conduction calculations

NASA Astrophysics Data System (ADS)

Solomon, Gemma C.; Reimers, Jeffrey R.; Hush, Noel S.

2005-06-01

In the calculation of conduction through single molecule's approximations about the geometry and electronic structure of the system are usually made in order to simplify the problem. Previously [G. C. Solomon, J. R. Reimers, and N. S. Hush, J. Chem. Phys. 121, 6615 (2004)], we have shown that, in calculations employing cluster models for the electrodes, proper treatment of the open-shell nature of the clusters is the most important computational feature required to make the results sensitive to variations in the structural and chemical features of the system. Here, we expand this and establish a general hierarchy of requirements involving treatment of geometrical approximations. These approximations are categorized into two classes: those associated with finite-dimensional methods for representing the semi-infinite electrodes, and those associated with the chemisorption topology. We show that ca. 100 unique atoms are required in order to properly characterize each electrode: using fewer atoms leads to nonsystematic variations in conductivity that can overwhelm the subtler changes. The choice of binding site is shown to be the next most important feature, while some effects that are difficult to control experimentally concerning the orientations at each binding site are actually shown to be insignificant. Verification of this result provides a general test for the precision of computational procedures for molecular conductivity. Predictions concerning the dependence of conduction on substituent and other effects on the central molecule are found to be meaningful only when they exceed the uncertainties of the effects associated with binding-site variation.

PAREMD: A parallel program for the evaluation of momentum space properties of atoms and molecules

NASA Astrophysics Data System (ADS)

Meena, Deep Raj; Gadre, Shridhar R.; Balanarayan, P.

2018-03-01

The present work describes a code for evaluating the electron momentum density (EMD), its moments and the associated Shannon information entropy for a multi-electron molecular system. The code works specifically for electronic wave functions obtained from traditional electronic structure packages such as GAMESS and GAUSSIAN. For the momentum space orbitals, the general expression for Gaussian basis sets in position space is analytically Fourier transformed to momentum space Gaussian basis functions. The molecular orbital coefficients of the wave function are taken as an input from the output file of the electronic structure calculation. The analytic expressions of EMD are evaluated over a fine grid and the accuracy of the code is verified by a normalization check and a numerical kinetic energy evaluation which is compared with the analytic kinetic energy given by the electronic structure package. Apart from electron momentum density, electron density in position space has also been integrated into this package. The program is written in C++ and is executed through a Shell script. It is also tuned for multicore machines with shared memory through OpenMP. The program has been tested for a variety of molecules and correlated methods such as CISD, Møller-Plesset second order (MP2) theory and density functional methods. For correlated methods, the PAREMD program uses natural spin orbitals as an input. The program has been benchmarked for a variety of Gaussian basis sets for different molecules showing a linear speedup on a parallel architecture.

Selective molecular transport through the protein shell of a bacterial microcompartment organelle

DOE PAGES

Chowdhury, Chiranjit; Chun, Sunny; Pang, Allan; ...

2015-02-23

Bacterial microcompartments are widespread prokaryotic organelles that have important and diverse roles ranging from carbon fixation to enteric pathogenesis. Current models for microcompartment function propose that their outer protein shell is selectively permeable to small molecules, but whether a protein shell can mediate selective permeability and how this occurs are unresolved questions. In this paper, biochemical and physiological studies of structure-guided mutants are used to show that the hexameric PduA shell protein of the 1,2-propanediol utilization (Pdu) microcompartment forms a selectively permeable pore tailored for the influx of 1,2-propanediol (the substrate of the Pdu microcompartment) while restricting the efflux ofmore » propionaldehyde, a toxic intermediate of 1,2-propanediol catabolism. Crystal structures of various PduA mutants provide a foundation for interpreting the observed biochemical and phenotypic data in terms of molecular diffusion across the shell. Finally and overall, these studies provide a basis for understanding a class of selectively permeable channels formed by nonmembrane proteins.« less

A new approach to the method of source-sink potentials for molecular conduction

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

Pickup, Barry T., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Fowler, Patrick W., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Borg, Martha

2015-11-21

We re-derive the tight-binding source-sink potential (SSP) equations for ballistic conduction through conjugated molecular structures in a form that avoids singularities. This enables derivation of new results for families of molecular devices in terms of eigenvectors and eigenvalues of the adjacency matrix of the molecular graph. In particular, we define the transmission of electrons through individual molecular orbitals (MO) and through MO shells. We make explicit the behaviour of the total current and individual MO and shell currents at molecular eigenvalues. A rich variety of behaviour is found. A SSP device has specific insulation or conduction at an eigenvalue ofmore » the molecular graph (a root of the characteristic polynomial) according to the multiplicities of that value in the spectra of four defined device polynomials. Conduction near eigenvalues is dominated by the transmission curves of nearby shells. A shell may be inert or active. An inert shell does not conduct at any energy, not even at its own eigenvalue. Conduction may occur at the eigenvalue of an inert shell, but is then carried entirely by other shells. If a shell is active, it carries all conduction at its own eigenvalue. For bipartite molecular graphs (alternant molecules), orbital conduction properties are governed by a pairing theorem. Inertness of shells for families such as chains and rings is predicted by selection rules based on node counting and degeneracy.« less

Retrieving transient conformational molecular structure information from inner-shell photoionization of laser-aligned molecules

DOE PAGES

Wang, Xu; Le, Anh -Thu; Yu, Chao; ...

2016-03-30

We discuss a scheme to retrieve transient conformational molecular structure information using photoelectron angular distributions (PADs) that have averaged over partial alignments of isolated molecules. The photoelectron is pulled out from a localized inner-shell molecular orbital by an X-ray photon. We show that a transient change in the atomic positions from their equilibrium will lead to a sensitive change in the alignment-averaged PADs, which can be measured and used to retrieve the former. Exploiting the experimental convenience of changing the photon polarization direction, we show that it is advantageous to use PADs obtained from multiple photon polarization directions. Lastly, amore » simple single-scattering model is proposed and benchmarked to describe the photoionization process and to do the retrieval using a multiple-parameter fitting method.« less

Size-Tunable and Functional Core-Shell Structured Silica Nanoparticles for Drug Release

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

Chi, Fangli; Guo, Ya Nan; Liu, Jun

2010-02-18

Size-tunable silica cross-linked micellar core-shell nanoparticles (SCMCSNs) were successfully synthesized from a Pluronic nonionic surfactant (F127) template system with organic swelling agents such as 1,3,5-trimethylbenzene (TMB) and octanoic acid at room temperature. The size and morphology of SCMCSNs were directly evidenced by TEM imaging and DLS measurements (up to ~90 nm). Pyrene and coumarin 153 (C153) were used as fluorescent probe molecules to investigate the effect and location of swelling agent molecules. Papaverine as a model drug was used to measure the loading capacity and release property of nanoparticles. The swelling agents can enlarge the nanoparticle size and improve themore » drug loading capacity of nanoparticles. Moreover, the carboxylic acid group of fatty acid can adjust the release behavior of the nanoparticles.« less

Multiconfiguration pair-density functional theory for doublet excitation energies and excited state geometries: the excited states of CN.

PubMed

Bao, Jie J; Gagliardi, Laura; Truhlar, Donald G

2017-11-15

Multiconfiguration pair-density functional theory (MC-PDFT) is a post multiconfiguration self-consistent field (MCSCF) method with similar performance to complete active space second-order perturbation theory (CASPT2) but with greater computational efficiency. Cyano radical (CN) is a molecule whose spectrum is well established from experiments and whose excitation energies have been used as a testing ground for theoretical methods to treat excited states of open-shell systems, which are harder and much less studied than excitation energies of closed-shell singlets. In the present work, we studied the adiabatic excitation energies of CN with MC-PDFT. Then we compared this multireference (MR) method to some single-reference (SR) methods, including time-dependent density functional theory (TDDFT) and completely renormalized equation-of-motion coupled-cluster theory with singles, doubles and noniterative triples [CR-EOM-CCSD(T)]; we also compared to some other MR methods, including configuration interaction singles and doubles (MR-CISD) and multistate CASPT2 (MS-CASPT2). Through a comparison between SR and MR methods, we achieved a better appreciation of the need to use MR methods to accurately describe higher excited states, and we found that among the MR methods, MC-PDFT stands out for its accuracy for the first four states out of the five doublet states studied this paper; this shows its efficiency for calculating doublet excited states.

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures

NASA Astrophysics Data System (ADS)

Khan, U.; Li, W. J.; Adeela, N.; Irfan, M.; Javed, K.; Wan, C. H.; Riaz, S.; Han, X. F.

2016-03-01

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3&cmb.macr;. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ~25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07946b

Biomineralization of Schlumbergerella floresiana, a significant carbonate-producing benthic foraminifer

NASA Astrophysics Data System (ADS)

Sabbatini, Anna; Bédouet, Laurent; Marie, Arul; Bartolini, Annachiara; Landemarre, Ludovic; Weber, Michele; Ngurah Kade Mahardika, Gusti; Berland, Sophie; Zito, Francesca; Vénec-Peyré, Marie-Thérèse

2016-04-01

Most foraminifera that produce a shell are efficient biomineralizers. They contribute to the global carbon cycle, and thus influence ocean-climate regulation. Calcification in foraminifera is likely biologically controlled and is potentially similar to shell formation in metazoan taxa (e.g. mollusks, corals, sea urchins). However, foraminiferal biomineralization processes and the molecules involved are still poorly understood. We analyzed the calcitic shell of the large tropical benthic foraminifer Schlumbergerella floresiana. We found a suite of macromolecules containing many charged and polar amino acids and glycine that are also abundant in biomineralization proteins of other phyla. As neither genomic nor transcriptomic data are available for foraminiferal biomineralization yet, de novo-generated sequences, obtained from organic matrices submitted to MS BLAST database search, led to the characterization of 156 peptides. Very few homologous proteins were matched in the proteomic database, implying that the peptides are derived from unknown proteins present in the foraminiferal organic matrices. The amino acid distribution of these peptides was queried against the UNIPROT database and the mollusk UNIPROT database for comparison. The mollusks compose a well-studied phylum that yield a large variety of biomineralization proteins. These results showed that proteins extracted from S. floresiana shells contained sequences enriched with glycine, alanine, and proline, making a set of residues that provided a signature unique to foraminifera. Three of the de novo peptides exhibited sequence similarities to peptides found in proteins such as pre-collagen-P and a group of P-type ATPases including a calcium-transporting ATPase. Surprisingly, the peptide that was most similar to the collagen-like protein was a glycine-rich peptide reported from the test and spine proteome of sea urchin. The molecules, identified by matrix-assisted laser desorption ionization-time of flight mass spectrometry analyses, included acid-soluble N-glycoproteins with its sugar moieties represented by high-mannose-type glycans and carbohydrates. Describing the nature of the proteins, and associated molecules in the skeletal structure of living foraminifera, can elucidate the biomineralization mechanisms of these major carbonate producers in marine ecosystems. Foraminifera constitute an important tool used for paleo-environmental reconstructions because of their nearly continuous fossil record and abundance. Many studies focus on their biomineralization process using a geochemical perspective to record environmental and climate changes from shell isotopic and trace element compositions. Our results are a first step toward understanding the functioning mechanism behind biomineralization and the molecules involved. Coupling geochemical and biological perspectives will enhance interpretation of the proxies used for climatic reconstructions and improve future modeling efforts.

Experimental investigation of mode I fracture for brittle tube-shaped particles

NASA Astrophysics Data System (ADS)

Stasiak, Marta; Combe, Gaël; Desrues, Jacques; Richefeu, Vincent; Villard, Pascal; Armand, Gilles; Zghondi, Jad

2017-06-01

We focus herein on the mechanical behavior of highly crushable grains. The object of our interest, named shell, is a hollow cylinder grain with ring cross-section, made of baked clay. The objective is to model the fragmentation of such shells, by means of discrete element (DE) approach. To this end, fracture modes I (opening fracture) and II (in-plane shear fracture) have to be investigated experimentally. This paper is essentially dedicated to mode I fracture. Therefore, a campaign of Brazilian-like compression tests, that result in crack opening, has been performed. The distribution of the occurrence of tensile strength is shown to obey a Weibull distribution for the studied shells, and Weibull's modulus was quantified. Finally, an estimate of the numerical/physical parameters required in a DE model (local strength), is proposed on the basis of the energy required to fracture through a given surface in mode I or II.

Self-assembly of core-shell structure PtO2@Pt nanodots and their formation evolution

NASA Astrophysics Data System (ADS)

Yang, Weijia; Liu, Junjie; Liu, Mingquan; Zhao, Zhicheng; Song, Yapeng; Tang, Xiufeng; Luo, Jianyi; Zeng, Qingguang; He, Xin

2018-05-01

Core-shell structure PtO2@Pt nanodots have been self-assembly by vacuum sputtering and high temperature annealing. First, Pt thin films with a small amount of PtO2 are grown on the sapphire substrates by vacuum sputtering. And then high temperature annealing on the thin films is carried out at 800 °C for 2 min to form Pt nanodots. During the cooling process, the atmosphere is deployed to supplant the nitrogen. Finally, even distributed core-shell structure PtO2@Pt nanodots with a diameter from 100 to 300 nm are achieved. Furthermore, the formation evolution of core-shell structure PtO2@Pt nanodots is also proposed. This work open up a new approach for fabricating core-shell structure nanodots.

An experimental point of view on hydration/solvation in halophilic proteins

PubMed Central

Talon, Romain; Coquelle, Nicolas; Madern, Dominique; Girard, Eric

2014-01-01

Protein-solvent interactions govern the behaviors of proteins isolated from extreme halophiles. In this work, we compared the solvent envelopes of two orthologous tetrameric malate dehydrogenases (MalDHs) from halophilic and non-halophilic bacteria. The crystal structure of the MalDH from the non-halophilic bacterium Chloroflexus aurantiacus (Ca MalDH) solved, de novo, at 1.7 Å resolution exhibits numerous water molecules in its solvation shell. We observed that a large number of these water molecules are arranged in pentagonal polygons in the first hydration shell of Ca MalDH. Some of them are clustered in large networks, which cover non-polar amino acid surface. The crystal structure of MalDH from the extreme halophilic bacterium Salinibacter ruber (Sr) solved at 1.55 Å resolution shows that its surface is strongly enriched in acidic amino acids. The structural comparison of these two models is the first direct observation of the relative impact of acidic surface enrichment on the water structure organization between a halophilic protein and its non-adapted counterpart. The data show that surface acidic amino acids disrupt pentagonal water networks in the hydration shell. These crystallographic observations are discussed with respect to halophilic protein behaviors in solution PMID:24600446

An experimental point of view on hydration/solvation in halophilic proteins.

PubMed

Talon, Romain; Coquelle, Nicolas; Madern, Dominique; Girard, Eric

2014-01-01

Protein-solvent interactions govern the behaviors of proteins isolated from extreme halophiles. In this work, we compared the solvent envelopes of two orthologous tetrameric malate dehydrogenases (MalDHs) from halophilic and non-halophilic bacteria. The crystal structure of the MalDH from the non-halophilic bacterium Chloroflexus aurantiacus (Ca MalDH) solved, de novo, at 1.7 Å resolution exhibits numerous water molecules in its solvation shell. We observed that a large number of these water molecules are arranged in pentagonal polygons in the first hydration shell of Ca MalDH. Some of them are clustered in large networks, which cover non-polar amino acid surface. The crystal structure of MalDH from the extreme halophilic bacterium Salinibacter ruber (Sr) solved at 1.55 Å resolution shows that its surface is strongly enriched in acidic amino acids. The structural comparison of these two models is the first direct observation of the relative impact of acidic surface enrichment on the water structure organization between a halophilic protein and its non-adapted counterpart. The data show that surface acidic amino acids disrupt pentagonal water networks in the hydration shell. These crystallographic observations are discussed with respect to halophilic protein behaviors in solution.

Lego Bricks and the Octet Rule: Molecular Models for Biochemical Pathways with Plastic, Interlocking Toy Bricks

ERIC Educational Resources Information Center

Lin, Henry J.; Lehoang, Jennifer; Kwan, Isabel; Baghaee, Anita; Prasad, Priya; Ha-Chen, Stephanie J.; Moss, Tanesha; Woods, Jeremy D.

2018-01-01

The 8 studs on a 2 × 4 Lego brick conveniently represent the outer shell of electrons for carbon, nitrogen, and oxygen atoms. We used Lego bricks to model these atoms, which are then joined together to form molecules by following the Lewis octet rule. A variety of small biological molecules can be modeled in this way, such as most amino acids,…

Three-dimensional six-connecting organic building blocks based on polychlorotriphenylmethyl units--synthesis, self-assembly, and magnetic properties.

PubMed

Roques, Nans; Maspoch, Daniel; Wurst, Klaus; Ruiz-Molina, Daniel; Rovira, Concepció; Veciana, Jaume

2006-12-13

The synthesis of a three-dimensional, six-connecting, organic building block based on a robust, rigid, and open-shell polychlorotriphenylmethyl (PTM) unit (radical 1) is reported, and its self-assembly properties are described in detail. The tendencies of this highly polar molecule and its hydrogenated precursor, compound 4, to form hydrogen bonds with oxygenated solvents ([1THF(6)] and [4THF(6)]) were reduced by replacing THF with diethyl ether in the crystallization process to yield two-dimensional (2D) hydrogen-bonded structures ([1(Et(2)O)(3)] and [4(Et(2)O)(3)]). The presence of direct hydrogen bonds between the radicals in the latter phase of 1 gives rise to very weak ferromagnetic intermolecular interactions at low temperatures, whereas when the radicals are isolated by THF molecules these interactions are antiferromagnetic and very weak. The role played by the carboxylic groups not only in the self-assembly properties but also in the transmission of the magnetic interactions has been illustrated by determination of the crystal structure and measurement of the magnetic properties of the corresponding hexaester radical 6, in which the close packing of molecular units gives rise to weak antiferromagnetic intermolecular interactions. Attempts to avoid solvation of the molecules in the solid state and to increase the structural and magnetic dimensionality were pursued by recrystallization of both compounds 1 and 4 from concentrated nitric acid, affording two three-dimensional (3D) robust hydrogen-bonded structures. While the structure obtained with compound 4 is characterized by the presence of polar channels and boxes containing water guest molecules along the c axis, radical 1 was oxidized to the corresponding fuchsone 10, which presented a completely different close-packed, guest-free structure.

Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory

PubMed Central

Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-ichi; Sugimoto, Naoki

2015-01-01

In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water–water interactions, (ii) ethylene glycol more effectively disrupted water–water interactions around Watson–Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson–Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. PMID:26538600

Acute cold stress improved the transcription of pro-inflammatory cytokines of Chinese soft-shelled turtle against Aeromonas hydrophila.

PubMed

Zhang, Zuobing; Chen, Bojian; Yuan, Lin; Niu, Cuijuan

2015-03-01

Chinese soft-shelled turtle, Pelodiscus sinensis, is widely cultured in East and Southeast Asian countries. It frequently encounters the stress of abrupt temperature changes, which leads to mass death in most cases. However, the mechanism underlying the stress-elicited death remains unknown. We have suspected that the stress impaired the immune function of Chinese soft-shelled turtle, which could result in the mass death, as we noticed that there was a clinical syndrome of infection in dead turtles. To test our hypothesis, we first performed bioinformatic annotation of several pro-inflammatory molecules (IL-1β, TNFα, IL-6, IL-12β) of Chinese soft-shelled turtle. Then, we treated the turtles in six groups, injected with Aeromonas hydrophila before acute cold stress (25 °C) and controls, after acute cold stress (15 °C) and controls as well as after the temperature was restored to 25 °C and controls, respectively. Subsequently, real-time PCR for several pro-inflammatory cytokines (IL-1β, TNFα, IL-6, IL-12β, IL-8 and IFNγ) was performed to assess the turtle immune function in spleen and intestine, 24 hours after the injection. We found that the mRNA expression levels of the immune molecules were all enhanced after acute cold stress. This change disappeared when the temperature was restored back to 25 °C. Our results suggest that abrupt temperature drop did not suppress the immune function of Chinese soft-shelled turtle in response to germ challenge after abrupt temperature drop. In contrast, it may even increase the expression of various cytokines at least, within a short time after acute cold stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

Real-time observation of valence electron motion.

PubMed

Goulielmakis, Eleftherios; Loh, Zhi-Heng; Wirth, Adrian; Santra, Robin; Rohringer, Nina; Yakovlev, Vladislav S; Zherebtsov, Sergey; Pfeifer, Thomas; Azzeer, Abdallah M; Kling, Matthias F; Leone, Stephen R; Krausz, Ferenc

2010-08-05

The superposition of quantum states drives motion on the atomic and subatomic scales, with the energy spacing of the states dictating the speed of the motion. In the case of electrons residing in the outer (valence) shells of atoms and molecules which are separated by electronvolt energies, this means that valence electron motion occurs on a subfemtosecond to few-femtosecond timescale (1 fs = 10(-15) s). In the absence of complete measurements, the motion can be characterized in terms of a complex quantity, the density matrix. Here we report an attosecond pump-probe measurement of the density matrix of valence electrons in atomic krypton ions. We generate the ions with a controlled few-cycle laser field and then probe them through the spectrally resolved absorption of an attosecond extreme-ultraviolet pulse, which allows us to observe in real time the subfemtosecond motion of valence electrons over a multifemtosecond time span. We are able to completely characterize the quantum mechanical electron motion and determine its degree of coherence in the specimen of the ensemble. Although the present study uses a simple, prototypical open system, attosecond transient absorption spectroscopy should be applicable to molecules and solid-state materials to reveal the elementary electron motions that control physical, chemical and biological properties and processes.

Origin of the blueshift of water molecules at interfaces of hydrophilic cyclic compounds

PubMed Central

Tomobe, Katsufumi; Yamamoto, Eiji; Kojić, Dušan; Sato, Yohei; Yasui, Masato; Yasuoka, Kenji

2017-01-01

Water molecules at interfaces of materials exhibit enigmatic properties. A variety of spectroscopic studies have observed a high-frequency motion in these water molecules, represented by a blueshift, at both hydrophobic and hydrophilic interfaces. However, the molecular mechanism behind this blueshift has remained unclear. Using Raman spectroscopy and ab initio molecular dynamics simulations, we reveal the molecular mechanism of the blueshift of water molecules around six monosaccharide isomers. In the first hydration shell, we found weak hydrogen-bonded water molecules that cannot have a stable tetrahedral water network. In the water molecules, the vibrational state of the OH bond oriented toward the bulk solvent strongly contributes to the observed blueshift. Our work suggests that the blueshift in various solutions originates from the vibrational motions of these observed water molecules. PMID:29282448

Laser-triggered release of encapsulated molecules from polylactic-co-glycolic acid microcapsules

NASA Astrophysics Data System (ADS)

Ariyasu, Kazumasa; Ishii, Atsuhiro; Umemoto, Taiga; Terakawa, Mitsuhiro

2016-08-01

The controlled release of encapsulated molecules from a microcapsule is a promising method of targeted drug delivery. Laser-triggered methods for the release of encapsulated molecules have the advantage of spatial and temporal controllability. In this study, we demonstrated the release of encapsulated molecules from biodegradable polymer-based microcapsules using near-infrared femtosecond laser pulses. The polylactic-co-glycolic acid microcapsules encapsulating fluorescein isothiocyanate-dextran molecules were fabricated using a dual-coaxial nozzle system. Irradiation of femtosecond laser pulses enhanced the release of the molecules from the microcapsules, which was accompanied by a decrease in the residual ratio of the microcapsules. The laser-induced modification of the surface of the shell of the microcapsules indicated the potential for sustained release as well as burst release.

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Bauschlicher, Charles W., Jr.; Allamandola, Louis J.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

PubMed Central

Sutton, Rebecca; Sposito, Garrison

2002-01-01

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs+ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs+ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs+ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs+ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.

Large-Scale Trade in Legally Protected Marine Mollusc Shells from Java and Bali, Indonesia

PubMed Central

Nijman, Vincent; Spaan, Denise; Nekaris, K. Anne-Isola

2015-01-01

Background Tropical marine molluscs are traded globally. Larger species with slow life histories are under threat from over-exploitation. We report on the trade in protected marine mollusc shells in and from Java and Bali, Indonesia. Since 1987 twelve species of marine molluscs are protected under Indonesian law to shield them from overexploitation. Despite this protection they are traded openly in large volumes. Methodology/Principal Findings We collected data on species composition, origins, volumes and prices at two large open markets (2013), collected data from wholesale traders (2013), and compiled seizure data by the Indonesian authorities (2008–2013). All twelve protected species were observed in trade. Smaller species were traded for 32,000 shells valued at USD500,000), chambered nautilus (Nautilus pompilius) (>3,000 shells, USD60,000) and giant clams (Tridacna spp.) (>2,000 shells, USD45,000) were traded in largest volumes. Two-thirds of this trade was destined for international markets, including in the USA and Asia-Pacific region. Conclusions/Significance We demonstrated that the trade in protected marine mollusc shells in Indonesia is not controlled nor monitored, that it involves large volumes, and that networks of shell collectors, traders, middlemen and exporters span the globe. This impedes protection of these species on the ground and calls into question the effectiveness of protected species management in Indonesia; solutions are unlikely to be found only in Indonesia and must involve the cooperation of importing countries. PMID:26717021

Report on the 18th International Conference on X-ray and Inner-Shell Processes (X99).

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

Gemmell, D. S.; Physics

2000-01-01

The 18th conference of the series served as a forum for discussing fundamental issues in the field of x-ray and inner-shell processes and their application in various disciplines of science and technology. Special emphasis was given to the opportunities offered by modern synchrotron x-ray sources. The program included plenary talks, progress reports and poster presentations relating to new developments in the field of x-ray and inner-shell processes. The range of topics included: X-ray interactions with atoms, molecules, clusters, surfaces and solids; Decay processes for inner-shell vacancies; X-ray absorption and emission spectroscopy - Photoionization processes; Phenomena associated with highly charged ionsmore » and collisions with energetic particles; Electron-spin and -momentum spectroscopy; X-ray scattering and spectroscopy in the study of magnetic systems; Applications in materials science, biology, geosciences, and other disciplines; Elastic and inelastic x-ray scattering processes in atoms and molecules; Threshold phenomena (post-collision interaction, resonant Raman processes, etc.); Nuclear absorption and scattering of x-rays; 'Fourth-generation' x-ray sources; Processes exploiting the polarization and coherence properties of x-ray beams; Developments in experimental techniques (x-ray optics, temporal techniques, detectors); Microscopy, spectromicroscopy, and various imaging techniques; Non-linear processes and x-ray lasers; Ionization and excitation induced by charged particles and by x-rays; and Exotic atoms (including 'hollow' atoms and atoms that contain 'exotic' particles).« less

Triple-functional core-shell structured upconversion luminescent nanoparticles covalently grafted with photosensitizer for luminescent, magnetic resonance imaging and photodynamic therapy in vitro

NASA Astrophysics Data System (ADS)

Qiao, Xiao-Fei; Zhou, Jia-Cai; Xiao, Jia-Wen; Wang, Ye-Fu; Sun, Ling-Dong; Yan, Chun-Hua

2012-07-01

Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF4:Yb,Er@CaF2@SiO2-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF4:Yb,Er@CaF2 nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd3+ ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r1) and similar imaging effect.Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF4:Yb,Er@CaF2@SiO2-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF4:Yb,Er@CaF2 nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd3+ ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r1) and similar imaging effect. Electronic supplementary information (ESI) available: More TEM, emission spectra, longitudinal and transverse relaxation times, t2-weighted MR images of the as-prepared nanomaterial, and confocal fluorescent images of HeLa cells. See DOI: 10.1039/c2nr30938f

Facile method for preparing organic/inorganic hybrid capsules using amino-functional silane coupling agent in aqueous media.

PubMed

Kurayama, Fumio; Suzuki, Satoru; Oyamada, Tetsuro; Furusawa, Takeshi; Sato, Masahide; Suzuki, Noboru

2010-09-01

A new and facile method for preparing microcapsules with 3-aminopropyltriethoxysilane (APTES)/alginate hybrid shell (AP-capsule) is proposed based on gelling and sol-gel processes. In this method, conventional capsules with alginate shells (Alg-capsule) are produced by dripping carboxymethyl cellulose solution containing calcium chloride into a sodium alginate solution. Subsequently, addition of the Alg-capsules to an aqueous APTES solution induces the formation of APTES/alginate hybrid shells. The optical observation shows that the texture of AP-capsules is more glossy and transparent than that of Alg-capsules. The surface morphology and elemental composition of microcapsules were characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). The results suggest that APTES molecules are incorporated to the framework of the alginate shells via electrostatic interaction between amino groups of APTES and carboxyl groups of alginate and the hybrid shells have a dense and homogeneous structure. In the formation reaction, the shrinking of the capsule shells occurs and the accumulation of APTES in the capsule shells proceeds with pseudo first-order kinetics. Moreover, these behaviors are greatly influenced by pH of the reaction solution, especially promoted under acidic and alkaline conditions. Copyright 2010 Elsevier Inc. All rights reserved.

The IPEA dilemma in CASPT2† †Electronic supplementary information (ESI) available: Original data (Table S1) and additional comments for the literature survey; note on symmetry (Table S2), geometries (Table S3), data (Tables S4–S6) and comments (Section S2) for calculations on di-/triatomic molecules; results (Tables S7–S25) and comments (Section S3) for calculations on the organic molecular data set. See DOI: 10.1039/c6sc03759c Click here for additional data file.

PubMed Central

Zobel, J. Patrick

2017-01-01

Multi-configurational second order perturbation theory (CASPT2) has become a very popular method for describing excited-state properties since its development in 1990. To account for systematic errors found in the calculation of dissociation energies, an empirical correction applied to the zeroth-order Hamiltonian, called the IPEA shift, was introduced in 2004. The errors were attributed to an unbalanced description of open-shell versus closed-shell electronic states and is believed to also lead to an underestimation of excitation energies. Here we show that the use of the IPEA shift is not justified and the IPEA should not be used to calculate excited states, at least for organic chromophores. This conclusion is the result of three extensive analyses. Firstly, we survey the literature for excitation energies of organic molecules that have been calculated with the unmodified CASPT2 method. We find that the excitation energies of 356 reference values are negligibly underestimated by 0.02 eV. This value is an order of magnitude smaller than the expected error based on the calculation of dissociation energies. Secondly, we perform benchmark full configuration interaction calculations on 137 states of 13 di- and triatomic molecules and compare the results with CASPT2. Also in this case, the excited states are underestimated by only 0.05 eV. Finally, we perform CASPT2 calculations with different IPEA shift values on 309 excited states of 28 organic small and medium-sized organic chromophores. We demonstrate that the size of the IPEA correction scales with the amount of dynamical correlation energy (and thus with the size of the system), and gets immoderate already for the molecules considered here, leading to an overestimation of the excitation energies. It is also found that the IPEA correction strongly depends on the size of the basis set. The dependency on both the size of the system and of the basis set, contradicts the idea of a universal IPEA shift which is able to compensate for systematic CASPT2 errors in the calculation of excited states. PMID:28572908

SERS microscopy: plasmonic nanoparticle probes and biomedical applications

NASA Astrophysics Data System (ADS)

Gellner, M.; Schütz, M.; Salehi, M.; Packeisen, J.; Ströbel, P.; Marx, A.; Schmuck, C.; Schlücker, S.

2010-08-01

Nanoparticle probes for use in targeted detection schemes and readout by surface-enhanced Raman scattering (SERS) comprise a metal core, Raman reporter molecules and a protective shell. One design of SERS labels specifically optimized for biomedical applications in conjunction with red laser excitation is based on tunable gold/silver nanoshells, which are completely covered by a self-assembled monolayer (SAM) of Raman reporters. A shell around the SAM-coated metal core stabilizes the colloid and prevents particle aggregation. The optical properties and SERS efficiencies of these plasmonic nanostructures are characterized both experimentally and theoretically. Subsequent bioconjugation of SERS probes to ligands such as antibodies is a prerequisite for the selective detection of the corresponding target molecule via the characteristic Raman signature of the label. Biomedical imaging applications of SERS-labeled antibodies for tumor diagnostics by SERS microscopy are presented, using the localization of the tumor suppressor p63 in prostate tissue sections as an example.

Ultrafast isomerization initiated by X-ray core ionization

NASA Astrophysics Data System (ADS)

Liekhus-Schmaltz, Chelsea E.; Tenney, Ian; Osipov, Timur; Sanchez-Gonzalez, Alvaro; Berrah, Nora; Boll, Rebecca; Bomme, Cedric; Bostedt, Christoph; Bozek, John D.; Carron, Sebastian; Coffee, Ryan; Devin, Julien; Erk, Benjamin; Ferguson, Ken R.; Field, Robert W.; Foucar, Lutz; Frasinski, Leszek J.; Glownia, James M.; Gühr, Markus; Kamalov, Andrei; Krzywinski, Jacek; Li, Heng; Marangos, Jonathan P.; Martinez, Todd J.; McFarland, Brian K.; Miyabe, Shungo; Murphy, Brendan; Natan, Adi; Rolles, Daniel; Rudenko, Artem; Siano, Marco; Simpson, Emma R.; Spector, Limor; Swiggers, Michele; Walke, Daniel; Wang, Song; Weber, Thorsten; Bucksbaum, Philip H.; Petrovic, Vladimir S.

2015-09-01

Rapid proton migration is a key process in hydrocarbon photochemistry. Charge migration and subsequent proton motion can mitigate radiation damage when heavier atoms absorb X-rays. If rapid enough, this can improve the fidelity of diffract-before-destroy measurements of biomolecular structure at X-ray-free electron lasers. Here we study X-ray-initiated isomerization of acetylene, a model for proton dynamics in hydrocarbons. Our time-resolved measurements capture the transient motion of protons following X-ray ionization of carbon K-shell electrons. We Coulomb-explode the molecule with a second precisely delayed X-ray pulse and then record all the fragment momenta. These snapshots at different delays are combined into a `molecular movie' of the evolving molecule, which shows substantial proton redistribution within the first 12 fs. We conclude that significant proton motion occurs on a timescale comparable to the Auger relaxation that refills the K-shell vacancy.

Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

2016-09-01

Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

Chemical Understanding of the Limited Site-Specificity in Molecular Inner-Shell Photofragmentation

DOE PAGES

Inhester, Ludger; Oostenrijk, Bart; Patanen, Minna; ...

2018-02-14

In many cases fragmentation of molecules upon inner-shell ionization is very unspecific with respect to the initially localized ionization site. Often this finding is interpreted in terms of an equilibration of internal energy into vibrational degrees of freedom after Auger decay. In this paper, we investigate the X-ray photofragmentation of ethyl trifluoroacetate upon core electron ionization at environmentally distinct carbon sites using photoelectron–photoion–photoion coincidence measurements and ab initio electronic structure calculations. For all four carbon ionization sites, the Auger decay weakens the same bonds and transfers the two charges to opposite ends of the molecule, which leads to a rapidmore » dissociation into three fragments, followed by further fragmentation steps. Finally, the lack of site specificity is attributed to the character of the dicationic electronic states after Auger decay instead of a fast equilibration of internal energy.« less

X-ray and simulation studies of water

NASA Astrophysics Data System (ADS)

Nilsson, A.; Schlesinger, D.; G. M. Pettersson, L.

Here we present a picture that combines discussions regarding the thermodynamic anomalies in ambient and supercooled water with recent interpretations of X-ray spectroscopy and scattering data of water. At ambient temperatures most molecules favor a closer packing than tetrahedral, with strongly distorted hydrogen bonds, which allows the quantized librational modes to be excited and contribute to the entropy, but with enthalpically favored tetrahedrally bonded water patches appearing as fluctuations, a competition between entropy and enthalpy. Upon cooling water the amount of molecules participating in tetrahedral structures and the size of the tetrahedral patches increase. The two local structures are connected to the liquid-liquid critical point hypothesis in supercooled water corresponding to high-density liquid (HDL) and low-density liquid (LDL). We demonstrate that the HDL local structure deviates from a tetrahedral coordination not only through a collapse of the 2nd shell but also through severe distortions around the 1st coordination shell.

The problem of hole localization in inner-shell states of N2 and CO2 revisited with complete active space self-consistent field approach.

PubMed

Rocha, Alexandre B; de Moura, Carlos E V

2011-12-14

Potential energy curves for inner-shell states of nitrogen and carbon dioxide molecules are calculated by inner-shell complete active space self-consistent field (CASSCF) method, which is a protocol, recently proposed, to obtain specifically converged inner-shell states at multiconfigurational level. This is possible since the collapse of the wave function to a low-lying state is avoided by a sequence of constrained optimization in the orbital mixing step. The problem of localization of K-shell states is revisited by calculating their energies at CASSCF level based on both localized and delocalized orbitals. The localized basis presents the best results at this level of calculation. Transition energies are also calculated by perturbation theory, by taking the above mentioned MCSCF function as zeroth order wave function. Values for transition energy are in fairly good agreement with experimental ones. Bond dissociation energies for N(2) are considerably high, which means that these states are strongly bound. Potential curves along ground state normal modes of CO(2) indicate the occurrence of Renner-Teller effect in inner-shell states. © 2011 American Institute of Physics

Impact of straight, unconnected, radially-oriented, and tapered mesopores on column efficiency: A theoretical investigation.

PubMed

Gritti, Fabrice

2017-02-17

Superficially porous particles (SPPs) can be prepared from a pseudomorphic transformation (PMT) which produces straight, unconnected, and radially-oriented mesopores (ROMs). ROMs can be either both ends open in fully porous particles (FPPs) or one-end-closed in SPPs. The impact of ROMs on the longitudinal diffusion (B/u), solid-liquid mass transfer resistance (C s u), and on the eddy dispersion (A(u)) height equivalent to a theoretical plate (HETP) of 3D randomly packed columns was investigated based on theoretical viewpoints. Torquato's theory of effective diffusion in packed beds (B term), Giddings' coupling theory of eddy dispersion (A term), and Giddings' generalized nonequilibrium theory (C s term) are applied to make predictions. First, it is found that the A term is nearly independent on the internal structure of the particle. Secondly, in the absence of flow, infinitely narrow and both ends open (no constriction effect) ROMs induce an internal hindrance factor of 23 regarding diffusion along the axial direction. Experimental data reveal that one-end-closed and 80Å wide ROMs in SPPs lead to a measurable internal hindrance factor of 27 regarding diffusion in the porous shell. Thirdly, above the optimum speed, the C s coefficient is dependent on the geometry (cylinders, cones, etc.) of the ROMs: when ROMs are conical in SPPs, C s is expected to decrease by 80% with respect to cylindrical ROMs. From an application perspective, PMT-SPPs prepared with narrow ROMs are well suited for the analysis of small molecules at or below optimum speed (lowest B term) while PMT-SPPs made of wide and conical ROMs are ideal for the analysis of large molecules above optimum speed (smallest C s term). Copyright © 2017. Published by Elsevier B.V.

Quantum mechanical calculations of charge effects on gating the KcsA channel.

PubMed

Kariev, Alisher M; Znamenskiy, Vasiliy S; Green, Michael E

2007-05-01

A series of ab initio (density functional) calculations were carried out on side chains of a set of amino acids, plus water, from the (intracellular) gating region of the KcsA K(+) channel. Their atomic coordinates, except hydrogen, are known from X-ray structures [D.A. Doyle, J.M. Cabral, R.A. Pfuetzner, A. Kuo, J.M. Gulbis, S.L. Cohen, B.T. Chait, R. MacKinnon, The structure of the potassium channel: molecular basis of K(+) conduction and selectivity, Science 280 (1998) 69-77; R. MacKinnon, S.L. Cohen, A. Kuo, A. Lee, B.T. Chait, Structural conservation in prokaryotic and eukaryotic potassium channels, Science 280 (1998) 106-109; Y. Jiang, A. Lee, J. Chen, M. Cadene, B.T. Chait, R. MacKinnon, The open pore conformation of potassium channels. Nature 417 (2001) 523-526], as are the coordinates of some water oxygen atoms. The 1k4c structure is used for the starting coordinates. Quantum mechanical optimization, in spite of the starting configuration, places the atoms in positions much closer to the 1j95, more tightly closed, configuration. This state shows four water molecules forming a "basket" under the Q119 side chains, blocking the channel. When a hydrated K(+) approaches this "basket", the optimized system shows a strong set of hydrogen bonds with the K(+) at defined positions, preventing further approach of the K(+) to the basket. This optimized structure with hydrated K(+) added shows an ice-like 12 molecule nanocrystal of water. If the water molecules exchange, unless they do it as a group, the channel will remain blocked. The "basket" itself appears to be very stable, although it is possible that the K(+) with its hydrating water molecules may be more mobile, capable of withdrawing from the gate. It is also not surprising that water essentially freezes, or forms a kind of glue, in a nanometer space; this agrees with experimental results on a rather different, but similarly sized (nm dimensions) system [K.B. Jinesh, J.W.M. Frenken, Capillary condensation in atomic scale friction: how water acts like a glue, Phys. Rev. Lett. 96 (2006) 166103/1-4]. It also agrees qualitatively with simulations on channels [A. Anishkin, S. Sukharev, Water dynamics and dewetting transitions in the small mechanosensitive channel MscS, Biophys. J. 86 (2004) 2883-2895; O. Beckstein, M.S.P. Sansom, Liquid-vapor oscillations of water in hydrophobic nanopores, Proc. Natl Acad. Sci. U. S. A. 100 (2003) 7063-7068] and on featureless channel-like systems [J. Lu, M.E. Green, Simulation of water in a pore with charges: application to a gating mechanism for ion channels, Prog. Colloid Polym. Sci. 103 (1997) 121-129], in that it forms a boundary on water that is not obvious from the liquid state. The idea that a structure is stable, even if individual molecules exchange, is well known, for example from the hydration shell of ions. We show that when charges are added in the form of protons to the domains (one proton per domain), the optimized structure is open. No stable water hydrogen bonds hold it together; an opening of 11.0 A appears, measured diagonally between non-neighboring domains as glutamine 119 carbonyl O-O distance. This is comparable to the opening in the MthK potassium channel structure that is generally agreed to be open. The appearance of the opening is in rather good agreement with that found by Perozo and coworkers. In contrast, in the uncharged structure this diagonal distance is 6.5 A, and the water "basket" constricts the uncharged opening still further, with the ice-like structure that couples the K(+) ion to the gating region freezing the entrance to the channel. Comparison with our earlier model for voltage gated channels suggests that a similar mechanism may apply in those channels.

A contact algorithm for shell problems via Delaunay-based meshing of the contact domain

NASA Astrophysics Data System (ADS)

Kamran, K.; Rossi, R.; Oñate, E.

2013-07-01

The simulation of the contact within shells, with all of its different facets, represents still an open challenge in Computational Mechanics. Despite the effort spent in the development of techniques for the simulation of general contact problems, an all-seasons algorithm applicable to complex shell contact problems is yet to be developed. This work focuses on the solution of the contact between thin shells by using a technique derived from the particle finite element method together with a rotation-free shell triangle. The key concept is to define a discretization of the contact domain (CD) by constructing a finite element mesh of four-noded tetrahedra that describes the potential contact volume. The problem is completed by using an assumed-strain approach to define an elastic contact strain over the CD.

High-value utilization of egg shell to synthesize Silver and Gold-Silver core shell nanoparticles and their application for the degradation of hazardous dyes from aqueous phase-A green approach.

PubMed

Sinha, Tanur; Ahmaruzzaman, M

2015-09-01

The common household material, egg shell of Anas platyrhynchos is utilized for the synthesis of Silver and Gold-Silver core shell nanoparticles using greener, environment friendly and economic way. The egg shell extracts were acting as a stabilizing and reducing agents. This method avoids the use of external reducing and stabilizing agents, templates and solvents. The effects of various reaction parameters, such as reaction temperature, concentration in the formation of nanoparticles have also been investigated. The compositional abundance of gelatin may be envisaged for the effective reductive as well as stabilizing potency. The mechanisms for the formation of NPs have also been presented. The synthesized Ag NPs formed were predominantly spherical in nature with an average size of particles in the range of 6-26 nm. While, Au-Ag core shell nanoparticles formed were spherical and oval shaped, within a narrow size spectrum of 9-18 nm. Both the Ag NPs Au-and Ag core shell nanoparticles showed characteristic Bragg's reflection planes of fcc structure and surface plasmon resonance at 430 nm and 365 nm, respectively. The NPs were utilized for the removal of toxic and hazardous dyes, such as Rose Bengal, Methyl Violet 6 B and Methylene Blue from aqueous phase. Approximately 98.2%, 98.4% and 97% degradations of Rose Bengal, Methyl Violet 6 B, and Methylene Blue were observed with Ag NPs, while the percentage degradation of these dyes was 97.3%, 97.6% and 96% with Au-Ag NPs, respectively. Therefore, the present study has opened up an innovative way for synthesizing Ag NPs and Au-Ag bimetallic nanostructures of different morphologies and sizes involving the utilization of egg shell extract. The high efficiency of the NPs as photocatalysts has opened a promising application for the removal of hazardous dyes from the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.

Nuclear quantum effects in water exchange around lithium and fluoride ions

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

Wilkins, David M.; Manolopoulos, David; Dang, Liem X.

2015-02-14

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain reasonably good agreement with experimental data for solutions of lithium by augmenting the Coulombic interactions between the ion and the water molecules with a standard Lennard-Jones ion-oxygen potential, the same is not true for solutions of fluoride, for which we find that a potential with a softer repulsive wall gives much better agreement. A small degree of destabilization of the first hydration shell ismore » found in quantum simulations of both ions when compared with classical simulations, with the shell becoming less sharply defined and the mean residence time of the water molecules in the shell decreasing. In line with these modest differences, we find that the mechanisms of the water exchange reactions are unaffected by quantization, so a classical description of these reactions gives qualitatively correct and quantitatively reasonable results. We also find that the quantum effects in solutions of lithium are larger than in solutions of fluoride. This is partly due to the stronger interaction of lithium with water molecules, partly due to the lighter mass of lithium, and partly due to competing quantum effects in the hydration of fluoride, which are absent in the hydration of lithium. LXD was supported by US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.« less

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Vertical Electron Detachment Energies for Octahedral Closed-Shell Multiply Charged Anions

DTIC Science & Technology

1994-04-22

however, at low theoretical levels, motivating us to extend the investigations to: a) higher levels of theory, b) analogous closed-shell singly- and...hundredths of an eV. This further supports our choice of SBKJ+diff as the basis set for the production runs. The SCF relaxation energies for F- and Cl...intensities for the product molecules ML 5(’)" (D3h) and ML 4 (n-2 )" 15 (Td) were determined at the SCF/SBKJ level and are reported in Table V

Thermal annealing dynamics of carbon-coated LiFePO4 nanoparticles studied by in-situ analysis

NASA Astrophysics Data System (ADS)

Krumeich, Frank; Waser, Oliver; Pratsinis, Sotiris E.

2016-10-01

The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO4-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO4-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO4 starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further to T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO4 particles (diameter in the range 300-400 nm), in agreement with ex-situ experiments.

Shell-Isolated Tip-Enhanced Raman and Fluorescence Spectroscopy.

PubMed

Huang, Ya-Ping; Huang, Sheng-Chao; Wang, Xiang-Jie; Bodappa, Nataraju; Li, Chao-Yu; Yin, Hao; Su, Hai-Sheng; Meng, Meng; Zhang, Hua; Ren, Bin; Yang, Zhi-Lin; Zenobi, Renato; Tian, Zhong-Qun; Li, Jian-Feng

2018-06-18

Tip-enhanced Raman spectroscopy can provide molecular fingerprint information with ultrahigh spatial resolution, but the tip will be easily contaminated, thus leading to artifacts. It also remains a great challenge to establish tip-enhanced fluorescence because of the quenching resulting from the proximity of the metal tip. Herein, we report shell-isolated tip-enhanced Raman and fluorescence spectroscopies by employing ultrathin shell-isolated tips fabricated by atomic layer deposition. Such shell-isolated tips not only show outstanding electromagnetic field enhancement in TERS but also exclude interference by contaminants, thus greatly promoting applications in solution. Tip-enhanced fluorescence has also been achieved using these shell-isolated tips, with enhancement factors of up to 1.7×10 3 , consistent with theoretical simulations. Furthermore, tip-enhanced Raman and fluorescence signals are acquired simultaneously, and their relative intensities can be manipulated by changing the shell thickness. This work opens a new avenue for ultrahigh resolution surface analysis using plasmon-enhanced spectroscopies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular and isotopic composition of lipids in modern and fossil bivalve shells: Records of paleoenvironmental change?

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

CoBabe, E.A.

1995-12-31

Suites of lipids residing in situ in modern and fossil bivalve shells offer new possibilities for the study of paleoecology and paleoclimatology. Distributions of carbon isotopic compositions of modem shell lipids suggests that many of these compounds, including alkanes, sterols, fatty acids, ketones and phytadienes, are derived from the bivalves and not directly from the surrounding environment. The occurrence of fatty acids in modem and fossil shell material opens up the possibility that saturation levels of these compounds may be used as paleothermometers. To date, the utility of fatty acids in paleoclimate studies has been limited because of the swiftmore » breakdown of these compounds in sediment. However, initial results indicate that fatty acids in bivalve shells retain their original structure for at least several million years. Comparison of modem bivalve shell fatty acids from tropical, temperate and polar nearshore marine systems will be presented, along with analogous fossil data.« less

Construction of homogenous/heterogeneous hollow mesoporous silica nanostructures by silica-etching chemistry: principles, synthesis, and applications.

PubMed

Chen, Yu; Chen, Hang-Rong; Shi, Jian-Lin

2014-01-21

Colloidal hollow mesoporous silica nanoparticles (HMSNs) are aspecial type of silica-based nanomaterials with penetrating mesopore channels on their shells. HMSNs exhibit unique structural characteristics useful for diverse applications: Firstly, the hollow interiors can function as reservoirs for enhanced loading of guest molecules, or as nanoreactors for the growth of nanocrystals or for catalysis in confined spaces. Secondly, the mesoporous silica shell enables the free diffusion of guest molecules through the intact shell. Thirdly, the outer silica surface is ready for chemical modifications, typically via its abundant Si-OH bonds. As early as 2003, researchers developed a soft-templating methodto prepare hollow aluminosilicate spheres with penetrating mesopores in a cubic symmetry pattern on the shells. However, adapting this method for applications on the nanoscale, especially for biomedicine, has proved difficult because the soft templating micelles are very sensitive to liquid environments, making it difficult to tune key parameters such as dispersity, morphology and structure. In this Account, we present the most recent developments in the tailored construction of highly dispersive and monosized HMSNs using simple silica-etching chemistry, and we discuss these particles' excellent performance in diverse applications. We first introduce general principles of silica-etching chemistry for controlling the chemical composition and the structural parameters (particle size, pore size, etching modalities, yolk-shell nanostructures, etc.) of HMSNs. Secondly, we include recent progress in constructing heterogeneous, multifunctional, hollow mesoporous silica nanorattles via several methods for diverse applications. These elaborately designed HMSNs could be topologically transformed to prepare hollow mesoporous carbon nanoparticles or functionalized to produce HMSN-based composite nanomaterials. Especially in biomedicine, HMSNs are excellent as carriers to deliver either hydrophilic or hydrophobic anti-cancer drugs, to tumor cells, offering enhanced chemotherapeutic efficacy and diminished toxic side effects. Most recently, research has shown that loading one or more anticancer drugs into HMSNs can inhibit metastasis or reverse multidrug resistance of cancer cells. HMSNs could also deliver hydrophobic perfluorohexane (PFH) molecules to improve high intensity focused ultrasound (HIFU) cancer surgery by changing the tissue acoustic environment; and HMSNs could act as nanoreactors for enhanced catalytic activity and/or durability. The versatility of silica-etching chemistry, a simple but scalable synthetic methodology, offers great potential for the creation of new types of HMSN-based nanostructures in a range of applications.

Insights into chromatographic separation using core-shell metal-organic frameworks: Size exclusion and polarity effects.

PubMed

Qin, Weiwei; Silvestre, Martin E; Kirschhöfer, Frank; Brenner-Weiss, Gerald; Franzreb, Matthias

2015-09-11

Porous metal-organic frameworks (MOFs) [Cu3(BTC)2(H2O)3]n (also known as HKUST-1; BTC, benzene-1,3,5-tricarboxylic acid) were synthesized as homogeneous shell onto carboxyl functionalized magnetic microparticles through a liquid phase epitaxy (LPE) process. The as-synthesized core-shell HKUST-1 magnetic microparticles composites were characterized by XRD and SEM, and used as stationary phase in high performance liquid chromatography (HPLC). The effects of the unique properties of MOFs onto the chromatographic performance are demonstrated by the experiments. First, remarkable separation of pyridine and bipyridine is achieved, although both molecules show a strong interaction between the Cu-ions in HKUST-1 and the nitrogen atoms in their heterocyles. The difference can be explained due to size exclusion of bipyridine from the well defined pore structure of crystalline HKUST-1. Second, the enormous variety of possible interactions of sample molecules with the metal ions and linkers within MOFs allows for specifically tailored solid phases for challenging separation tasks. For example, baseline separation of three chloroaniline (CLA) isomers tested can be achieved without the need for gradient elution modes. Along with the experimental HPLC runs, in-depth modelling with a recently developed chromatography modelling software (ChromX) was applied and proofs the software to be a powerful tool for exploring the separation potential of thin MOF films. The pore diffusivity of pyridine and CLA isomers within HKUST-1 are found to be around 2.3×10(-15)m(2)s(-1). While the affinity of HKUST-1 to the tested molecules strongly differs, the maximum capacities are in the same range, with 0.37molL(-1) for pyridine and 0.23molL(-1) for CLA isomers, corresponding to 4.0 and 2.5 molecules per MOF unit cell, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

The complex-scaled multiconfigurational spin-tensor electron propagator method for low-lying shape resonances in Be-, Mg- and Ca-

NASA Astrophysics Data System (ADS)

Tsogbayar, Tsednee; Yeager, Danny L.

2017-01-01

We further apply the complex scaled multiconfigurational spin-tensor electron propagator method (CMCSTEP) for the theoretical determination of resonance parameters with electron-atom systems including open-shell and highly correlated (non-dynamical correlation) atoms and molecules. The multiconfigurational spin-tensor electron propagator method (MCSTEP) developed and implemented by Yeager and his coworkers for real space gives very accurate and reliable ionization potentials and electron affinities. CMCSTEP uses a complex scaled multiconfigurational self-consistent field (CMCSCF) state as an initial state along with a dilated Hamiltonian where all of the electronic coordinates are scaled by a complex factor. CMCSTEP is designed for determining resonances. We apply CMCSTEP to get the lowest 2P (Be-, Mg-) and 2D (Mg-, Ca-) shape resonances using several different basis sets each with several complete active spaces. Many of these basis sets we employ have been used by others with different methods. Hence, we can directly compare results with different methods but using the same basis sets.

A data set from flash X-ray imaging of carboxysomes

NASA Astrophysics Data System (ADS)

Hantke, Max F.; Hasse, Dirk; Ekeberg, Tomas; John, Katja; Svenda, Martin; Loh, Duane; Martin, Andrew V.; Timneanu, Nicusor; Larsson, Daniel S. D.; van der Schot, Gijs; Carlsson, Gunilla H.; Ingelman, Margareta; Andreasson, Jakob; Westphal, Daniel; Iwan, Bianca; Uetrecht, Charlotte; Bielecki, Johan; Liang, Mengning; Stellato, Francesco; Deponte, Daniel P.; Bari, Sadia; Hartmann, Robert; Kimmel, Nils; Kirian, Richard A.; Seibert, M. Marvin; Mühlig, Kerstin; Schorb, Sebastian; Ferguson, Ken; Bostedt, Christoph; Carron, Sebastian; Bozek, John D.; Rolles, Daniel; Rudenko, Artem; Foucar, Lutz; Epp, Sascha W.; Chapman, Henry N.; Barty, Anton; Andersson, Inger; Hajdu, Janos; Maia, Filipe R. N. C.

2016-08-01

Ultra-intense femtosecond X-ray pulses from X-ray lasers permit structural studies on single particles and biomolecules without crystals. We present a large data set on inherently heterogeneous, polyhedral carboxysome particles. Carboxysomes are cell organelles that vary in size and facilitate up to 40% of Earth’s carbon fixation by cyanobacteria and certain proteobacteria. Variation in size hinders crystallization. Carboxysomes appear icosahedral in the electron microscope. A protein shell encapsulates a large number of Rubisco molecules in paracrystalline arrays inside the organelle. We used carboxysomes with a mean diameter of 115±26 nm from Halothiobacillus neapolitanus. A new aerosol sample-injector allowed us to record 70,000 low-noise diffraction patterns in 12 min. Every diffraction pattern is a unique structure measurement and high-throughput imaging allows sampling the space of structural variability. The different structures can be separated and phased directly from the diffraction data and open a way for accurate, high-throughput studies on structures and structural heterogeneity in biology and elsewhere.

Recent progress in density functional theory

NASA Astrophysics Data System (ADS)

Truhlar, Donald

2014-03-01

Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.

Better Finite-Element Analysis of Composite Shell Structures

NASA Technical Reports Server (NTRS)

Clarke, Gregory

2007-01-01

A computer program implements a finite-element-based method of predicting the deformations of thin aerospace structures made of isotropic materials or anisotropic fiber-reinforced composite materials. The technique and corresponding software are applicable to thin shell structures in general and are particularly useful for analysis of thin beamlike members having open cross-sections (e.g. I-beams and C-channels) in which significant warping can occur.

A Variational Method for Calculating the Natural Frequencies and Mode Shapes of a Cantilevered Open Cylindrical Shell.

DTIC Science & Technology

1983-12-01

A + f( (n xNxx Nx)6u + (nxNx 9 Nee)Sv )ds (19) s w1 where n are defined as the direction cosines between the normal and the y direction. To integrate...of a specific shell shape. Thus far, Eq (27) applies to all cylindrical shells with the only assumption being the thickness, h, is small as com - pared...results. For instance, after solving Eq (32) for its eight roots, one of them must be established as X1. While this choice is com - pletely arbitrary at

Theoretical analysis of bimetallic nanorod dimer biosensors for label-free molecule detection

NASA Astrophysics Data System (ADS)

Das, Avijit; Talukder, Muhammad Anisuzzaman

2018-02-01

In this work, we theoretically analyze a gold (Au) core within silver (Ag) shell (Au@Ag) nanorod dimer biosensor for label-free molecule detection. The incident light on an Au@Ag nanorod strongly couples to localized surface plasmon modes, especially around the tip region. The field enhancement around the tip of a nanorod or between the tips of two longitudinally aligned nanorods as in a dimer can be exploited for sensitive detection of biomolecules. We derive analytical expressions for the interactions of an Au@Ag nanorod dimer with the incident light. We also study the detail dynamics of an Au@Ag nanorod dimer with the incident light computationally using finite difference time domain (FDTD) technique when core-shell ratio, relative position of the nanorods, and angle of incidence of light change. We find that the results obtained using the developed analytical model match well with that obtained using FDTD simulations. Additionally, we investigate the sensitivity of the Au@Ag nanorod dimer, i.e., shift in the resonance wavelength, when a target biomolecule such as lysozyme (Lys), human serum albumin (HSA), anti-biotin (Abn), human catalase (CAT), and human fibrinogen (Fb) protein molecules are attached to the tips of the nanorods.

Core-shell AgSiO2-protoporphyrin IX nanoparticle: Effect of the Ag core on reactive oxygen species generation

NASA Astrophysics Data System (ADS)

Lismont, M.; Pá; ez-Martinez, C.; Dreesen, L.

2015-03-01

Photodynamic therapy (PDT) for cancer is based on the use of a light sensitive molecule to produce, under specific irradiation, toxic reactive oxygen species (ROS). A way to improve the therapy efficiency is to increase the amount of produced ROS near cancer cells. This aim can be achieved by using a metal enhanced process arising when an optically active molecule is located near a metallic nanoparticle (NP). Here, the coupling effect between silver (Ag) NPs and protoporphyrin IX (PpIX) molecules, a clinically approved photosensitizer, is studied compared first, to PpIX fluorescence yield and second, to ROS production efficiency. By applying a modified Stöber process, PpIX was encapsulated into a silica (SiO2) shell, surrounding a 60 nm sized Ag core. We showed that, compared to SiO2-PpIX NPs, Ag coated SiO2-PpIX NPs dramatically decreased PpIX fluorescence together with singlet oxygen production efficiency. However, after incubation time in the dark, the amount of superoxide anions generated by the Ag doped sample was higher than the control sample one.

Thermodynamic properties of water molecules in the presence of cosolute depend on DNA structure: a study using grid inhomogeneous solvation theory.

PubMed

Nakano, Miki; Tateishi-Karimata, Hisae; Tanaka, Shigenori; Tama, Florence; Miyashita, Osamu; Nakano, Shu-Ichi; Sugimoto, Naoki

2015-12-02

In conditions that mimic those of the living cell, where various biomolecules and other components are present, DNA strands can adopt many structures in addition to the canonical B-form duplex. Previous studies in the presence of cosolutes that induce molecular crowding showed that thermal stabilities of DNA structures are associated with the properties of the water molecules around the DNAs. To understand how cosolutes, such as ethylene glycol, affect the thermal stability of DNA structures, we investigated the thermodynamic properties of water molecules around a hairpin duplex and a G-quadruplex using grid inhomogeneous solvation theory (GIST) with or without cosolutes. Our analysis indicated that (i) cosolutes increased the free energy of water molecules around DNA by disrupting water-water interactions, (ii) ethylene glycol more effectively disrupted water-water interactions around Watson-Crick base pairs than those around G-quartets or non-paired bases, (iii) due to the negative electrostatic potential there was a thicker hydration shell around G-quartets than around Watson-Crick-paired bases. Our findings suggest that the thermal stability of the hydration shell around DNAs is one factor that affects the thermal stabilities of DNA structures under the crowding conditions. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Computational studies on self-assembled paclitaxel structures: templates for hierarchical block copolymer assemblies and sustained drug release.

PubMed

Guo, Xin D; Tan, Jeremy P K; Kim, Sung H; Zhang, Li J; Zhang, Ying; Hedrick, James L; Yang, Yi Y; Qian, Yu

2009-11-01

Paclitaxel-loaded poly(ethylene oxide)-b-poly(lactide) (PEO-b-PLA) systems have been observed to assemble into fiber structures with remarkably different properties using different chirality and molecular weight of PLA segments. In this study, dissipative particle dynamics (DPD) simulations were carried out to elaborate the microstructures and properties of pure paclitaxel and paclitaxel-loaded PEO-b-PLA systems. Paclitaxel molecules formed ribbon or fiber like structures in water. With the addition of PEO-b-PDLA, PEO-b-PLLA and their stereocomplex, paclitaxel acted as a template and polymer molecules assembled around the paclitaxel structure to form core/shell structured fibers having a PEO shell. For PEO19-b-PDLA27 and PEO19-b-PLLA27 systems, PLA segments and paclitaxel molecules were distributed homogeneously in the core of fibers based on the hydrophobic interactions. In the stereocomplex formulation, paclitaxel molecules were more concentrated in the inner PLA stereocomplex core, which led to slower release of paclitaxel. By increasing the length of PLA segments (e.g. 8,16,22 and 27), the crystalline structure of paclitaxel was gradually weakened and destroyed, which was further proved by X-ray diffraction studies. All the simulation results agreed well with experimental data, suggesting that the DPD simulations may provide a powerful tool for designing drug delivery systems.

Enhanced exchange bias and improved ferromagnetic properties in Permalloy-BiFe0.95Co0.05O3 core-shell nanostructures.

PubMed

Javed, K; Li, W J; Ali, S S; Shi, D W; Khan, U; Riaz, S; Han, X F

2015-12-14

Hybrid core-shell nanostructures consisting of permalloy (Ni80Fe20) and multiferroic(BiFeO3, BFO/BiFe0.95Co0.05O3, BFC) materials were synthesized by a two-step method, based on wet chemical impregnation and subsequent electrodeposition within porous alumina membranes. Structural and magnetic characterizations have been done to investigate doping effect on magnetic properties and exchange bias. The magnetometry analysis revealed significant enhancements of the exchange bias and coercivity in NiFe-BFC core-shell nanostructures as compared with NiFe-BFO core-shell nanostructures. The enhancements can be attributed to the effective reduction of ferromagnet domain sizes between adjacent layers of core-shell structure. It indicates that it is possible to improve properties of multiferroic composites by site-engineering method. Our approach opens a pathway to obtain optimized nanostructured multiferroic composites exhibiting tunable magnetic properties.

Enhanced exchange bias and improved ferromagnetic properties in Permalloy–BiFe0.95Co0.05O3 core–shell nanostructures

PubMed Central

Javed, K.; Li, W. J.; Ali, S. S.; Shi, D. W.; Khan, U.; Riaz, S.; Han, X. F.

2015-01-01

Hybrid core–shell nanostructures consisting of permalloy (Ni80Fe20) and multiferroic(BiFeO3, BFO/BiFe0.95Co0.05O3, BFC) materials were synthesized by a two-step method, based on wet chemical impregnation and subsequent electrodeposition within porous alumina membranes. Structural and magnetic characterizations have been done to investigate doping effect on magnetic properties and exchange bias. The magnetometry analysis revealed significant enhancements of the exchange bias and coercivity in NiFe-BFC core-shell nanostructures as compared with NiFe-BFO core-shell nanostructures. The enhancements can be attributed to the effective reduction of ferromagnet domain sizes between adjacent layers of core-shell structure. It indicates that it is possible to improve properties of multiferroic composites by site-engineering method. Our approach opens a pathway to obtain optimized nanostructured multiferroic composites exhibiting tunable magnetic properties. PMID:26658956

A pathway for the growth of core-shell Pt-Pd nanoparticles

DOE PAGES

Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; ...

2015-10-12

In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joiningmore » together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.« less

Magnetic response of hybrid ferromagnetic and antiferromagnetic core-shell nanostructures.

PubMed

Khan, U; Li, W J; Adeela, N; Irfan, M; Javed, K; Wan, C H; Riaz, S; Han, X F

2016-03-21

The synthesis of FeTiO3-Ni(Ni80Fe20) core-shell nanostructures by a two-step method (sol-gel and DC electrodeposition) has been demonstrated. XRD analysis confirms the rhombohedral crystal structure of FeTiO3(FTO) with space group R3[combining macron]. Transmission electron microscopy clearly depicts better morphology of nanostructures with shell thicknesses of ∼25 nm. Room temperature magnetic measurements showed significant enhancement of magnetic anisotropy for the permalloy (Ni80Fe20)-FTO over Ni-FTO core-shell nanostructures. Low temperature magnetic measurements of permalloy-FeTiO3 core-shell structure indicated a strong exchange bias mechanism with magnetic coercivity below the antiferromagnetic Neel temperature (TN = 59 K). The exchange bias is attributed to the alignment of magnetic moments in the antiferromagnetic material at low temperature. Our scheme opens a path towards optimum automotive systems and wireless communications wherein broader bandwidths and smaller sizes are required.

Generalized Stone-Wales transformation as the possible origin of ferromagnetism in polymeric C60: a density-functional theory study.

PubMed

Ribas-Ariño, J; Novoa, Juan J

2006-11-07

Recently, there has been a proposal [Y.-H. Kim et al., Phys. Rev. B 68, 125420 (2003)] suggesting that ferromagnetic interactions in compressed and heated polymeric-C(60) solids could be due to the existence of triplet open cages resulting from successive generalized Stone-Wales transformations within the C(60) cage. Here, by performing B3LYP3-21G and B3LYP6-31G(d) optimizations, we carried out a systematic investigation of the thermodynamics and kinetics of the mechanism of generation of these open cages in their closed-shell singlet, open-shell singlet, and triplet states. We also computed the magnetic interactions induced by the open cages presenting a triplet ground state. Our results indicate that this mechanism is not appropriate to explain the ferromagnetism found in compressed and heated polymeric C(60) for the following reasons: (a) the formation of the only open cage presenting a triplet ground state requires overpassing a highest energy point of 318 kcal/mol, well above other competitive mechanisms reported in the literature; the triplet open cages formed are not stable against their transformation into a diamagnetic intermediate; (c) the magnetic interactions between two adjacent triplet open cages are antiferromagnetic.

Synthesis and characterization of carbon nanotube from coconut shells activated carbon

NASA Astrophysics Data System (ADS)

Melati, A.; Hidayati, E.

2016-03-01

Carbon nanotubes (CNTs) have been explored in almost every single cancer treatment modality, including drug delivery, lymphatic targeted chemotherapy, photodynamic therapy, and gene therapy. They are considered as one of the most promising nanomaterial with the capability of both detecting the cancerous cells and delivering drugs or small therapeutic molecules to the cells. CNTs have unique physical and chemical properties such as high aspect ratio, ultralight weight, high mechanical strength, high electrical conductivity, and high thermal conductivity. Coconut Shell was researched as active carbon source on 500 - 600°C. These activated carbon was synthesized becomes carbon nanotube and have been proposed as a promising tool for detecting the expression of indicative biological molecules at early stage of cancer. Clinically, biomarkers cancer can be detected by CNT Biosensor. We are using pyrolysis methods combined with CVD process or Wet Chemical Process on 600°C. Our team has successfully obtained high purity, and aligned MWCNT (Multi Wall Nanotube) bundles on synthesis CNT based on coconut shells raw materials. CNTs can be used to cross the mammalian cell membrane by endocytosis or other mechanisms. SEM characterization of these materials have 179 nm bundles on phase 83° and their materials compound known by using FTIR characterization.

Anisotropic solvent model of the lipid bilayer. 1. Parameterization of long-range electrostatics and first solvation shell effects.

PubMed

Lomize, Andrei L; Pogozheva, Irina D; Mosberg, Henry I

2011-04-25

A new implicit solvation model was developed for calculating free energies of transfer of molecules from water to any solvent with defined bulk properties. The transfer energy was calculated as a sum of the first solvation shell energy and the long-range electrostatic contribution. The first term was proportional to solvent accessible surface area and solvation parameters (σ(i)) for different atom types. The electrostatic term was computed as a product of group dipole moments and dipolar solvation parameter (η) for neutral molecules or using a modified Born equation for ions. The regression coefficients in linear dependencies of solvation parameters σ(i) and η on dielectric constant, solvatochromic polarizability parameter π*, and hydrogen-bonding donor and acceptor capacities of solvents were optimized using 1269 experimental transfer energies from 19 organic solvents to water. The root-mean-square errors for neutral compounds and ions were 0.82 and 1.61 kcal/mol, respectively. Quantification of energy components demonstrates the dominant roles of hydrophobic effect for nonpolar atoms and of hydrogen-bonding for polar atoms. The estimated first solvation shell energy outweighs the long-range electrostatics for most compounds including ions. The simplicity and computational efficiency of the model allows its application for modeling of macromolecules in anisotropic environments, such as biological membranes.

Vacancy cascades in small molecules following x-ray inner shell photoionization

NASA Astrophysics Data System (ADS)

Ray, D.; Dunford, R. W.; Southworth, S. H.; Kanter, E. P.; Doumy, G.; Gao, Y.; Ho, P. J.; Picon, A.

2014-05-01

We are investigating molecular effects in vacancy cascades of small molecules containing heavy atoms - IBr, Br2 and CH2BrI - following K-shell ionization. In addition to fundamental interest in the physics of such decay processes, there are practical applications such as medical treatments that use energetic fragmentation of iodinated compounds with high energy x-rays to selectively treat tumorous cells. Other biological applications are also promising. We utilize the tunable monochromatic x-ray beam at the Advanced Photon Source to trigger K-shell photoionization of Br and I, and measure charge distributions and the kinetic energies released to the fragment ions. A newly designed detection device allows us to do multi-fold coincidence measurements involving momentum imaging of all the ion fragments with very high detection efficiency in coincidence with x-ray fluorescence detection. By comparing the molecular fragmentation probabilities and the kinetic energies released in Br2, IBr and CH2BrI we aim to gain understanding of the fragmentation mechanism as a function of the bond distance between I and Br. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

Solvation of Cr 3+ cation in water-acetonitrile mixture studied by IR spectroscopy: molecular penetration into the solvation shells

NASA Astrophysics Data System (ADS)

Jamróz, Dorota; Wójcik, Marek; Lindgren, Jan

2000-09-01

Infrared spectra of mixtures of water and deuteroacetonitrile containing the Cr 3+ cation have been studied as a function of concentration, time and temperature. The CN stretching vibration of CD 3CN molecules has been used as a probe of the structural environments. The CN band in the spectra of the solutions is a superposition of four subbands, which may be attributed to CD 3CN bound in the first, second, and third solvation shells of the cation and to non-bound CD 3CN. The character of changes of the integral intensities of the subbands with time for various H 2O:Cr 3+ molar ratios are explained by suggesting mechanisms of molecular replacement within the solvation shells of Cr 3+.

Electron affinity and excited states of methylglyoxal

NASA Astrophysics Data System (ADS)

Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

2017-07-01

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

Multicompartmental Microcapsules from Star Copolymer Micelles

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

Choi, Ikjun; Malak, Sidney T.; Xu, Weinan

2013-02-26

We present the layer-by-layer (LbL) assembly of amphiphilic heteroarm pH-sensitive star-shaped polystyrene-poly(2-pyridine) (PSnP2VPn) block copolymers to fabricate porous and multicompartmental microcapsules. Pyridine-containing star molecules forming a hydrophobic core/hydrophilic corona unimolecular micelle in acidic solution (pH 3) were alternately deposited with oppositely charged linear sulfonated polystyrene (PSS), yielding microcapsules with LbL shells containing hydrophobic micelles. The surface morphology and internal nanopore structure of the hollow microcapsules were comparatively investigated for shells formed from star polymers with a different numbers of arms (9 versus 22) and varied shell thickness (5, 8, and 11 bilayers). The successful integration of star unimers into themore » LbL shells was demonstrated by probing their buildup, surface segregation behavior, and porosity. The larger arm star copolymer (22 arms) with stretched conformation showed a higher increment in shell thickness due to the effective ionic complexation whereas a compact, uniform grainy morphology was observed regardless of the number of deposition cycles and arm numbers. Small-angle neutron scattering (SANS) revealed that microcapsules with hydrophobic domains showed different fractal properties depending upon the number of bilayers with a surface fractal morphology observed for the thinnest shells and a mass fractal morphology for the completed shells formed with the larger number of bilayers. Moreover, SANS provides support for the presence of relatively large pores (about 25 nm across) for the thinnest shells as suggested from permeability experiments. The formation of robust microcapsules with nanoporous shells composed of a hydrophilic polyelectrolyte with a densely packed hydrophobic core based on star amphiphiles represents an intriguing and novel case of compartmentalized microcapsules with an ability to simultaneously store different hydrophilic, charged, and hydrophobic components within shells.« less

Growth of juvenile Arctica islandica under experimental conditions

NASA Astrophysics Data System (ADS)

Witbaard, R.; Franken, R.; Visser, B.

1998-02-01

In two laboratory experiments, the effects of temperature and food availability on the growth of 10- to 23-mm high specimens of the bivalve Arctica islandica were estimated. Each experimental set-up consisted of 5 treatments in which either the food supply or the temperature differed. It was demonstrated that Arctica is able to grow at temperatures as low as 1°C. A tenfold increase of shell growth was observed at temperatures between 1° and 12°C. The greatest change in growth rate took place between 1° and 6°C. Average instantaneous shell growth varies between 0.0003 at 1°C to 0.0032/day at 12°C. The results suggest that temperature hardly affects the time spent in filtration, whereas particle density strongly influences that response. Starved animals at 9°C have their siphons open during only 12% of the time, whereas the siphons of optimally fed animals were open on average during 76% of the observations. Increased siphon activity corresponded to high shell and tissue growth. At 9°C, average shell growth at the optimum cell density of 20×106 cell/l was 3.1 mm corresponding to an instantaneous rate of 0.0026/day. An algal cell density ( Isochrysis galbana, Dunaliella marina) ranging between 5 and 7×106 cell/l is just enough to keep shells alive at 9°C. Carbon conversion efficiency at 9°C is estimated to vary between 11 and 14%.

Analytic first derivatives for a spin-adapted open-shell coupled cluster theory: Evaluation of first-order electrical properties

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

Datta, Dipayan, E-mail: datta@uni-mainz.de; Gauss, Jürgen, E-mail: gauss@uni-mainz.de

2014-09-14

An analytic scheme is presented for the evaluation of first derivatives of the energy for a unitary group based spin-adapted coupled cluster (CC) theory, namely, the combinatoric open-shell CC (COSCC) approach within the singles and doubles approximation. The widely used Lagrange multiplier approach is employed for the derivation of an analytical expression for the first derivative of the energy, which in combination with the well-established density-matrix formulation, is used for the computation of first-order electrical properties. Derivations of the spin-adapted lambda equations for determining the Lagrange multipliers and the expressions for the spin-free effective density matrices for the COSCC approachmore » are presented. Orbital-relaxation effects due to the electric-field perturbation are treated via the Z-vector technique. We present calculations of the dipole moments for a number of doublet radicals in their ground states using restricted open-shell Hartree-Fock (ROHF) and quasi-restricted HF (QRHF) orbitals in order to demonstrate the applicability of our analytic scheme for computing energy derivatives. We also report calculations of the chlorine electric-field gradients and nuclear quadrupole-coupling constants for the CCl, CH{sub 2}Cl, ClO{sub 2}, and SiCl radicals.« less

Electrical properties study under radiation of the 3D-open-shell-electrode detector

NASA Astrophysics Data System (ADS)

Liu, Manwen; Li, Zheng

2018-05-01

Since the 3D-Open-Shell-Electrode Detector (3DOSED) is proposed and the structure is optimized, it is important to study 3DOSED's electrical properties to determine the detector's working performance, especially in the heavy radiation environments, like the Large Hadron Collider (LHC) and it's upgrade, the High Luminosity (HL-LHC) at CERN. In this work, full 3D technology computer-aided design (TCAD) simulations have been done on this novel silicon detector structure. Simulated detector properties include the electric field distribution, the electric potential distribution, current-voltage (I-V) characteristics, capacitance-voltage (C-V) characteristics, charge collection property, and full depletion voltage. Through the analysis of calculations and simulation results, we find that the 3DOSED's electric field and potential distributions are very uniform, even in the tiny region near the shell openings with little perturbations. The novel detector fits the designing purpose of collecting charges generated by particle/light in a good fashion with a well defined funnel shape of electric potential distribution that makes these charges drifting towards the center collection electrode. Furthermore, by analyzing the I-V, C-V, charge collection property and full depletion voltage, we can expect that the novel detector will perform well, even in the heavy radiation environments.

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

NASA Astrophysics Data System (ADS)

Shishodia, Manmohan Singh; Juneja, Soniya

2016-05-01

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. The theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.

Blockade of mGluR5 in the nucleus accumbens shell but not core attenuates heroin seeking behavior in rats

PubMed Central

Lou, Zhong-ze; Chen, Ling-hong; Liu, Hui-feng; Ruan, Lie-min; Zhou, Wen-hua

2014-01-01

Aim: Glutamatergic neurotransmission in the nucleus accumbens (NAc) is crucial for the relapse to heroin seeking. The aim of this study was to determine whether mGluR5 in the NAc core or shell involved in heroin seeking behavior in rats. Methods: Male SD rats were self-administered heroin under a fixed-ratio 1 (FR1) reinforcement schedule for 14 d, and subsequently withdrawn for 2 weeks. The selective mGluR5 antagonist 2-methyl-6-phenylethynyl-pyridine (MPEP, 5, 15 and 50 nmol per side) was then microinjected into the NAc core or shell 10 min before a heroin-seeking test induced by context, cues or heroin priming. Results: Microinjection of MPEP into the NAc shell dose-dependently decreased the heroin seeking induced by context, cues or heroin priming. In contrast, microinjection of MPEP into the NAc core did not alter the heroin seeking induced by cues or heroin priming. In addition, microinjection with MPEP (15 nmol per side) in the NAc shell reversed both the percentage of open arms entries (OE%) and the percentage of time spent in open arms (OT%) after heroin withdrawal. Microinjection of MPEP (50 nmol per side) in the striatum as a control location did not affect the heroin seeking behavior. Microinjection of MPEP in the 3 locations did not change the locomotion activities. Conclusion: Blockade of mGluR5 in NAc shell in rats specifically suppresses the relapse to heroin-seeking and anxiety-like behavior, suggesting that mGluR5 antagonists may be a potential candidate for the therapy of heroin addiction. PMID:25399651

The formation of molecules in interstellar clouds from singly and multiply ionized atoms

NASA Technical Reports Server (NTRS)

Langer, W. D.

1978-01-01

The suggestion is considered that multiply ionized atoms produced by K- and L-shell X-ray ionization and cosmic-ray ionization can undergo ion-molecule reactions and also initiate molecule production. The role of X-rays in molecule production in general is discussed, and the contribution to molecule production of the C(+) radiative association with hydrogen is examined. Such gas-phase reactions of singly and multiply ionized atoms are used to calculate molecular abundances of carbon-, nitrogen-, and oxygen-bearing species. The column densities of the molecules are evaluated on the basis of a modified version of previously developed isobaric cloud models. It is found that reactions of multiply ionized carbon with H2 can contribute a significant fraction of the observed CH in diffuse interstellar clouds in the presence of diffuse X-ray structures or discrete X-ray sources and that substantial amounts of CH(+) can be produced under certain conditions.

Laboratory Detection of HSiCN and HSiNC

NASA Astrophysics Data System (ADS)

Sanz, M. Eugenia; McCarthy, Michael C.; Thaddeus, Patrick

2002-09-01

Two new silicon-bearing molecules, the closed-shell asymmetric tops cyanosilylene HSiCN and its isomer HSiNC, have been detected in a laboratory discharge by molecular beam Fourier transform microwave spectroscopy. The rotational spectra of the normal and deuterated isotopic species of both molecules have been analyzed to derive precise spectroscopic constants, which allow the astronomically most interesting transitions up to 120 GHz to be calculated to an accuracy better than 1 km s-1 in equivalent radial velocity. Both molecules are good candidates for astronomical detection, closely related in structure and composition to known astronomical molecules, and they are highly polar, with estimated dipole moments of 3.5 D for HSiCN and 2.5 D for HSiNC.

Stabilities of protonated water-ammonia clusters

NASA Astrophysics Data System (ADS)

Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

2018-05-01

Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

On the electrophilic character of molecules through its relation with electronegativity and chemical hardness.

PubMed

Islam, Nazmul; Ghosh, Dulal C

2012-01-01

Electrophilicity is an intrinsic property of atoms and molecules. It probably originates logistically with the involvement in the physical process of electrostatics of soaked charge in electronic shells and the screened nuclear charge of atoms. Motivated by the existing view of conceptual density functional theory that similar to electronegativity and hardness equalization, there should be a physical process of equalization of electrophilicity during the chemical process of formation of hetero nuclear molecules, we have developed a new theoretical scheme and formula for evaluating the electrophilicity of hetero nuclear molecules. A comparative study with available bench marking reveals that the hypothesis of electrophilicity and equalization, and the present method of evaluating equalized electrophilicity, are scientifically promising.

On the Electrophilic Character of Molecules Through Its Relation with Electronegativity and Chemical Hardness

PubMed Central

Islam, Nazmul; Ghosh, Dulal C.

2012-01-01

Electrophilicity is an intrinsic property of atoms and molecules. It probably originates logistically with the involvement in the physical process of electrostatics of soaked charge in electronic shells and the screened nuclear charge of atoms. Motivated by the existing view of conceptual density functional theory that similar to electronegativity and hardness equalization, there should be a physical process of equalization of electrophilicity during the chemical process of formation of hetero nuclear molecules, we have developed a new theoretical scheme and formula for evaluating the electrophilicity of hetero nuclear molecules. A comparative study with available bench marking reveals that the hypothesis of electrophilicity and equalization, and the present method of evaluating equalized electrophilicity, are scientifically promising. PMID:22408445

Synthesis, characterization, and 3D-FDTD simulation of Ag@SiO2 nanoparticles for shell-isolated nanoparticle-enhanced Raman spectroscopy.

PubMed

Uzayisenga, Viviane; Lin, Xiao-Dong; Li, Li-Mei; Anema, Jason R; Yang, Zhi-Lin; Huang, Yi-Fan; Lin, Hai-Xin; Li, Song-Bo; Li, Jian-Feng; Tian, Zhong-Qun

2012-06-19

Au-seed Ag-growth nanoparticles of controllable diameter (50-100 nm), and having an ultrathin SiO(2) shell of controllable thickness (2-3 nm), were prepared for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Their morphological, optical, and material properties were characterized; and their potential for use as a versatile Raman signal amplifier was investigated experimentally using pyridine as a probe molecule and theoretically by the three-dimensional finite-difference time-domain (3D-FDTD) method. We show that a SiO(2) shell as thin as 2 nm can be synthesized pinhole-free on the Ag surface of a nanoparticle, which then becomes the core. The dielectric SiO(2) shell serves to isolate the Raman-signal enhancing core and prevent it from interfering with the system under study. The SiO(2) shell also hinders oxidation of the Ag surface and nanoparticle aggregation. It significantly improves the stability and reproducibility of surface-enhanced Raman scattering (SERS) signal intensity, which is essential for SERS applications. Our 3D-FDTD simulations show that Ag-core SHINERS nanoparticles yield at least 2 orders of magnitude greater enhancement than Au-core ones when excited with green light on a smooth Ag surface, and thus add to the versatility of our SHINERS method.

Higher Order π-Conjugated Polycyclic Hydrocarbons with Open-Shell Singlet Ground State: Nonazethrene versus Nonacene.

PubMed

Huang, Rui; Phan, Hoa; Herng, Tun Seng; Hu, Pan; Zeng, Wangdong; Dong, Shao-Qiang; Das, Soumyajit; Shen, Yongjia; Ding, Jun; Casanova, David; Wu, Jishan

2016-08-17

Higher order acenes (i.e., acenes longer than pentacene) and extended zethrenes (i.e., zethrenes longer than zethrene) are theoretically predicted to have an open-shell singlet ground state, and the radical character is supposed to increase with extension of molecular size. The increasing radical character makes the synthesis of long zethrenes and acenes very challenging, and so far, the longest reported zethrene and acene derivatives are octazethrene and nonacene, respectively. In addition, there is a lack of fundamental understanding of the differences between these two closely related open-shell singlet systems. In this work, we report the first synthesis of a challenging nonazethrene derivative, HR-NZ, and its full structural and physical characterizations including variable temperature NMR, ESR, SQUID, UV-vis-NIR absorption and electrochemical measurements. Compound HR-NZ has an open-shell singlet ground state with a moderate diradical character (y0 = 0.48 based on UCAM-B3LYP calculation) and a small singlet-triplet gap (ΔES-T = -5.2 kcal/mol based on SQUID data), thus showing magnetic activity at room temperature. It also shows amphoteric redox behavior, with a small electrochemical energy gap (1.33 eV). Its electronic structure and physical properties are compared with those of Anthony's nonacene derivative JA-NA and other zethrene derivatives. A more general comparison between higher order acenes and extended zethrenes was also conducted on the basis of ab initio electronic structure calculations, and it was found that zethrenes and acenes have very different spatial localization of the unpaired electrons. As a result, a faster decrease of singlet-triplet energy gap and a faster increase of radical character with increase of the number of benzenoid rings were observed in zethrene series. Our studies reveal that spatial localization of the frontier molecular orbitals play a very important role on the nature of radical character as well as the excitation energy.

Experimental binding energies for the metal complexes [Mg(CH3OH)n](2+), [Ca(CH3OH)n](2+), and [Sr(CH3OH)n](2+) for n in the range 4-20.

PubMed

Bruzzi, E; Stace, A J

2014-10-09

A supersonic source of clusters has been used to prepare neutral complexes of methanol in association with an alkaline earth metal atom. From these complexes the following metal-containing dications have been generated through electron ionization: [Mg(CH3OH)n](2+), [Ca(CH3OH)n](2+), and [Sr(CH3OH)n](2+), and for n in the range 4-20, kinetic energy release measurements following the evaporation of a single molecule have been undertaken using a high resolution mass spectrometer. Using finite heat bath theory, these data have been transformed into binding energies for individual methanol molecules attached to each of the three cluster systems. In the larger complexes (n > 6) the results exhibit a consistent trend, whereby the experimental binding energy data for all three metal ions are similar, suggesting that the magnitude of the charge rather than charge density influences the strength of the interaction. From a comparison with data recorded previously for (CH3OH)nH(+) it is found that the 2+ charge on a metal ion has an effect on the binding energy of molecules in complexes containing up to 20 solvent molecules. The results recorded for [Ca(CH3OH)n](2+) show evidence of a very marked transition between n = 6 and 7, which is thought to coincide with the completion of a primary solvation shell and the onset of molecules starting to occupy a second and most probably a third shell.

Scrape on Endeavour's robotic arm during oxygen leak repairs

NASA Technical Reports Server (NTRS)

2002-01-01

KENNEDY SPACE CENTER, FLA. -- The opening shown here is the site where the honeycomb shell around Endeavour's robotic arm has been cut to inspect the arm. A scrape of the shell occurred while work platforms were being installed to gain access to repair the oxygen leak in the Shuttle's mid-body. Launch of Endeavour on mission STS-113 has been postponed until no earlier than Nov. 22.

Dual-Channel, Molecular-Sieving Core/Shell ZIF@MOF Architectures as Engineered Fillers in Hybrid Membranes for Highly Selective CO2 Separation.

PubMed

Song, Zhuonan; Qiu, Fen; Zaia, Edmond W; Wang, Zhongying; Kunz, Martin; Guo, Jinghua; Brady, Michael; Mi, Baoxia; Urban, Jeffrey J

2017-11-08

A novel core/shell porous crystalline structure was prepared using a large pore metal organic framework (MOF, UiO-66-NH 2 , pore size, ∼ 0.6 nm) as core surrounded by a small pore zeolitic imidazolate framework (ZIF, ZIF-8, pore size, ∼ 0.4 nm) through a layer-by-layer deposition method and subsequently used as an engineered filler to construct hybrid polysulfone (PSF) membranes for CO 2 capture. Compared to traditional fillers utilizing only one type of porous material with rigid channels (either large or small), our custom designed core/shell fillers possess clear advantages via pore engineering: the large internal channels of the UiO-66-NH 2 MOFs create molecular highways to accelerate molecular transport through the membrane, while the thin shells with small pores (ZIF-8) or even smaller pores generated at the interface by the imperfect registry between the overlapping pores of ZIF and MOF enhance molecular sieving thus serving to distinguish slightly larger N 2 molecules (kinetic diameter, 0.364 nm) from smaller CO 2 molecules (kinetic diameter, 0.33 nm). The resultant core/shell ZIF@MOF and as-prepared hybrid PSF membranes were characterized by transmission electron microscopy, X-ray diffraction, wide-angle X-ray scattering, scanning electron microscopy, Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, and contact angle tests. The dependence of the separation performance of the membranes on the MOF/ZIF ratio was also studied by varying the number of layers of ZIF coatings. The integrated PSF-ZIF@MOF hybrid membrane (40 wt % loading) with optimized ZIF coating cycles showed improved hydrophobicity and excellent CO 2 separation performance by simultaneously increasing CO 2 permeability (CO 2 permeability of 45.2 barrer, 710% higher than PSF membrane) and CO 2 /N 2 selectivity (CO 2 /N 2 selectivity of 39, 50% higher than PSF membrane), which is superior to most reported hybrid PSF membranes. The strategy of using dual-channel molecular sieving core/shell porous crystals in hybrid membranes thus provides a promising means for CO 2 capture from flue gas.

Valve assembly for use with high temperature and high pressure fluids

DOEpatents

De Feo, Angelo

1982-01-01

The valve assembly for use with high temperature and high pressure fluids has inner and outer spaced shells and a valve actuator support of inner and outer spaced members which are connected at their end portions to the inner and outer shells, respectively, to extend substantially normal to the longitudinal axis of the inner shell. A layer of resilient heat insulating material covers the outer surfaces of the inner shell and the inner actuator support member and is of a thickness to only occupy part of the spaces between the inner and outer shells and inner and outer actuator support members. The remaining portion of the space between the inner and outer shells and the space between the inner and outer members is substantially filled with a body of castable, rigid refractory material. A movable valve member is disposed in the inner shell. A valve actuator assembly is supported in the valve actuator support to extend into the inner shell for connection with the movable valve member for movement of the movable valve member to positions from a fully open to a fully closed position to control flow of fluid through the inner shell. An anchor mneans is disposed adjacent opposite sides of the axis of the valve actuator support and attached to the inner shell so that relative radial movement between the inner and outer shell is permitted by the layer of resilient heat insulating material and relative longitudinal movement of the inner shell to the outer shell is permitted in opposite directions from the anchor means to thereby maintain the functional integrity of the movable valve member by providing an area of the inner shell surrounding the movable valve member longitdinally stationary, but at the same time allowing radial movement.

Basis set and electron correlation effects on the polarizability and second hyperpolarizability of model open-shell π-conjugated systems

NASA Astrophysics Data System (ADS)

Champagne, Benoı̂t; Botek, Edith; Nakano, Masayoshi; Nitta, Tomoshige; Yamaguchi, Kizashi

2005-03-01

The basis set and electron correlation effects on the static polarizability (α) and second hyperpolarizability (γ) are investigated ab initio for two model open-shell π-conjugated systems, the C5H7 radical and the C6H8 radical cation in their doublet state. Basis set investigations evidence that the linear and nonlinear responses of the radical cation necessitate the use of a less extended basis set than its neutral analog. Indeed, double-zeta-type basis sets supplemented by a set of d polarization functions but no diffuse functions already provide accurate (hyper)polarizabilities for C6H8 whereas diffuse functions are compulsory for C5H7, in particular, p diffuse functions. In addition to the 6-31G*+pd basis set, basis sets resulting from removing not necessary diffuse functions from the augmented correlation consistent polarized valence double zeta basis set have been shown to provide (hyper)polarizability values of similar quality as more extended basis sets such as augmented correlation consistent polarized valence triple zeta and doubly augmented correlation consistent polarized valence double zeta. Using the selected atomic basis sets, the (hyper)polarizabilities of these two model compounds are calculated at different levels of approximation in order to assess the impact of including electron correlation. As a function of the method of calculation antiparallel and parallel variations have been demonstrated for α and γ of the two model compounds, respectively. For the polarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset methods bracket the reference value obtained at the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples level whereas the projected unrestricted second-order Møller-Plesset results are in much closer agreement with the unrestricted coupled cluster singles and doubles with a perturbative inclusion of the triples values than the projected unrestricted Hartree-Fock results. Moreover, the differences between the restricted open-shell Hartree-Fock and restricted open-shell second-order Møller-Plesset methods are small. In what concerns the second hyperpolarizability, the unrestricted Hartree-Fock and unrestricted second-order Møller-Plesset values remain of similar quality while using spin-projected schemes fails for the charged system but performs nicely for the neutral one. The restricted open-shell schemes, and especially the restricted open-shell second-order Møller-Plesset method, provide for both compounds γ values close to the results obtained at the unrestricted coupled cluster level including singles and doubles with a perturbative inclusion of the triples. Thus, to obtain well-converged α and γ values at low-order electron correlation levels, the removal of spin contamination is a necessary but not a sufficient condition. Density-functional theory calculations of α and γ have also been carried out using several exchange-correlation functionals. Those employing hybrid exchange-correlation functionals have been shown to reproduce fairly well the reference coupled cluster polarizability and second hyperpolarizability values. In addition, inclusion of Hartree-Fock exchange is of major importance for determining accurate polarizability whereas for the second hyperpolarizability the gradient corrections are large.

The structure of liquid water up to 360 MPa from x-ray diffraction measurements using a high Q-range and from molecular simulation

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

Skinner, L. B.; Galib, M.; Fulton, J. L.

2016-04-07

X-ray diffraction measurements of liquid water are reported at pressures up to 360 MPa corresponding to a density of 0.0373 molecules per Å3. The measurements were conducted at a spatial resolution corresponding to Qmax = 16 Å-1. The method of data analysis and measurement in this study follows the earlier benchmark results reported for water under ambient conditions having density of 0.0333 molecules per Å3 and Qmax = 20 Å-1 [J Chem Phys 138, 074506 (2013)]1 and at 70°C having density of 0.0327 molecules per Å3 and Qmax = 20 Å-1. [J Chem Phys 141, 214507 (2014)]2 The structure ofmore » water is very different at these three different T and P state points and thus they provide basis for evaluating the fidelity of molecular simulation. Measurements show that at 360 MPa, the 4 waters residing in the region between 2.3-3 Å are nearly unchanged: the peak position, shape and coordination number are nearly identical to their values under ambient conditions. However, in the region above 3 Å, large structural changes occur with the collapse of the well-defined 2nd shell and shifting of higher shells to shorter distances. The measured structure is compared to simulated structure using intermolecular potentials described by both first-principles methods (revPBE-D3) and classical potentials (TIP4P/2005 and mW). The DFT-based, revPBE-D3 provides the best overall representation of the ambient, high-temperature and high-pressure data while the TIP4P/2005 also captures the densification mechanism, whereby the non-bonded 5th nearest neighbor molecule, which encroaches the 1st shell at ambient pressure, is pushed further into the local tetrahedral arrangement at higher pressures by the more distant molecules filling the void space in the network between the 1st and 2nd shells. Acknowledgments: Thanks to Rick Spence and Doug Robinson for support with the beamline equipment at the Advanced Photon Source. The helpful comments of Valeria Molinero are acknowledged. This work was supported by the U.S. Department of Energy (DOE) office of Basic Energy Sciences grant Number BES DE-FG02-09ER46650 which supported, MD simulations, data analysis and manuscript preparation (LBS and JBP). DOE contract DE-AC02-06CH11357 supports operation of the Advanced Photon Source at Argonne National Laboratory. Work by JLF, MG, GSK and CJM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.« less

Bistable mixed-valence molecular architectures for bit storage

NASA Astrophysics Data System (ADS)

Guihery, Nathalie; Durand, Gérard; Lepetit, Marie-Bernadette

1994-05-01

The work examines the possible realization of bit storage at the molecular scale using mixed valence compounds i.e. the existence of two stable and degenerate forms associated with the 0 and 1 positions of the bit. The proposed systems are constituted of two donors (D) and acceptor (A), or one donor and two acceptors, juxtaposed in DAD or ADA architectures. Our proposals take advantage of the possibility of donor—acceptor complexes to exhibit either complete or partial charge transfer. The first system we propose has an essentially neutral ground state. However, the potential energy surface (PES) presents two degenerated minima associated with a partial charge transfer between the donor and one of the two acceptor molecules (A δ-D δ+1 A and AD δ+ A δ-). Systems presenting a complete charge transfer give rise to two stable, weakly coupled, and degenerate ionic electronic states, A - A + A and AD + A - for an ADA architecture and D + A -D and DA -D + for a DAD In these cases, the two forms differ by both their intramolecular geometries and the relative positions of their constituents. It seems rather difficult to conceive such bistable molecular systems using closed-shell molecules, while a donor radical and a closed-shell acceptor or an acceptor radical and closed-shell donor can generate very stable ionic states. It is assumed that the relative positions of the donor and acceptor molecules can be fixed using chemical bridges constituted of rigid or flexible ligands. The writing and reading processes are discussed for each system as well as the information stability when a large number of bits are juxtaposed on a surface.

Computational study of An-X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis.

PubMed

O'Brien, Kieran T P; Kaltsoyannis, Nikolas

2017-01-17

A systematic computational study of organoactinide complexes of the form [LAnX] n+ has been carried out using density functional theory, the quantum theory of atoms in molecules (QTAIM) and Ziegler-Rauk energy decomposition analysis (EDA) methods. The systems studied feature L = trans-calix[2]benzene[2]pyrrolide, An = Th(iv), Th(iii), U(iii) and X = BH 4 , BO 2 C 2 H 4 , Me, N(SiH 3 ) 2 , OPh, CH 3 , NH 2 , OH, F, SiH 3 , PH 2 , SH, Cl, CH 2 Ph, NHPh, OPh, SiH 2 Ph, PHPh 2 , SPh, CPh 3 , NPh 2 , OPh, SiPh 3 PPh 2 , SPh. The PBE0 hybrid functional proved most suitable for geometry optimisations based on comparisons with available experimental data. An-X bond critical point electron densities, energy densities and An-X delocalisation indices, calculated with the PBE functional at the PBE0 geometries, are correlated with An-X bond energies, enthalpies and with the terms in the EDA. Good correlations are found between energies and QTAIM metrics, particularly for the orbital interaction term, provided the X ligand is part of an isoelectronic series and the number of open shell electrons is low (i.e. for the present Th(iv) and Th(iii) systems).

Ion Association in AlCl3 Aqueous Solutions from Constrained First-Principles Molecular Dynamics

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

Cauet, Emilie L.; Bogatko, Stuart A.; Bylaska, Eric J.

2012-10-15

Ab initio molecular dynamics was used to investigate the ion pairing behavior between Cl- and the Al3+ ion in an aqueous AlCl3 solution containing 63 water molecules. A series of constrained simulations was carried out at 300 K for up to 16 ps each, by fixing the inter-nuclear separation (rAl-Cl) between the Al3+ ion and one of the Cl- ions. The calculated potential of mean force of the Al3+-Cl- ion pair shows a pronounced minimum at rAl-Cl = 2.3 Å corresponding to a contact ion pair (CIP). Two local minima assigned to solvent separated ion pairs (SSIP) are identified atmore » rAl-Cl= 4.4 and 6.0 Å. The positions of the free energy minima coincide with the hydration shell intervals of the Al3+ cation suggesting that the Cl- ion is inclined to reside in regions of low concentration of waters, i.e. between the 1st and 2nd shells of Al3+ and between the 2nd shell and bulk. A detailed analysis of solvent structure around the Al3+ and Cl- ions as a function of rAl-Cl is presented. The results are compared to structure data from X-ray measurements and unconstrained AIMD simulations of single ions Al3+ and Cl- and AlCl3 solutions. The dipole moment of the water molecules inside the 1st and 2nd hydration shells of Al3+ and in the bulk region and those of the Clion were calculated as a function of rAl-Cl. Major changes in the electronic structure of the system result from the removal of Cl- from the 1st hydration shell of the Al3+ cation. Finally, two unconstrained AIMD simulations of aqueous AlCl3 solutions corresponding to CIP and SSIP configurations were performed (17 ps, 300 K). Only minor structural changes are observed in these systems, confirming their stability.« less

Electronic stopping in oxides beyond Bragg additivity

NASA Astrophysics Data System (ADS)

Sigmund, P.; Schinner, A.

2018-01-01

We present stopping cross sections calculated by our PASS code for several ions in metal oxides and SiO2 over a wide energy range. Input takes into account changes in the valence structure by assigning two additional electrons to the 2p shell of oxygen and removing the appropriate number of electrons from the outer shells of the metal atom. Results are compared with tabulated experimental values and with two versions of Bragg's additivity rule. Calculated stopping cross sections are applied in testing a recently-proposed scaling rule, which relates the stopping cross section to the number of oxygen atoms per molecule.

Single-Enzyme Nanoparticles Armored by a Nanometer-Scale Organic/Inorganic Network

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

Kim, Jungbae; Grate, Jay W.

2003-09-01

We have developed armored single-enzyme nanoparticles (SENs), which dramatically stabilize a protease (a-chymotrypsin, CT) by surrounding each enzyme molecule with a porous composite organic/inorganic shell of less than a few nanometers thick. The armored enzymes show no decrease in CT activity at 30C for four days while free CT activity is rapidly reduced by orders of magnitude. The armored shell around CT is sufficiently thin and porous that it does not place any serious mass-transfer limitation on substrates. This unique approach will have a great impact in using enzymes in various fields.

Multilayered Polyelectrolyte Microcapsules: Interaction with the Enzyme Cytochrome C Oxidase

PubMed Central

Pastorino, Laura; Dellacasa, Elena; Noor, Mohamed R.; Soulimane, Tewfik; Bianchini, Paolo; D'Autilia, Francesca; Antipov, Alexei; Diaspro, Alberto; Tofail, Syed A. M.; Ruggiero, Carmelina

2014-01-01

Cell-sized polyelectrolyte capsules functionalized with a redox-driven proton pump protein were assembled for the first time. The interaction of polyelectrolyte microcapsules, fabricated by electrostatic layer-by-layer assembly, with cytochrome c oxidase molecules was investigated. We found that the cytochrome c oxidase retained its functionality, that the functionalized microcapsules interacting with cytochrome c oxidase were permeable and that the permeability characteristics of the microcapsule shell depend on the shell components. This work provides a significant input towards the fabrication of an integrated device made of biological components and based on specific biomolecular functions and properties. PMID:25372607

First Principles Simulations fo the Supercritical Behavior of Ore Forming Fluids

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

Weare, John H

2013-04-19

Abstract of Selected Research Progress: I. First-principles simulation of solvation structure and deprotonation reactions of ore forming metal ions in very nonideal solutions: Advances in algorithms and computational performance achieved in this grant period have allowed the atomic level dynamical simulation of complex nanoscale materials using interparticle forces calculated directly from an accurate density functional solution to the electronic Schr dinger equation (ab-initio molecular dynamics, AIMD). Focus of this program was on the prediction and analysis of the properties of environmentally important ions in aqueous solutions. AIMD methods have provided chemical interpretations of these very complex systems with an unprecedentedmore » level of accuracy and detail. The structure of the solvation region neighboring a highly charged metal ion (e.g., 3+) in an aqueous solution is very different from that of bulk water. The many-body behaviors (polarization, charge transfer, etc.) of the ion-water and water-water interactions in this region are difficult to capture with conventional empirical potentials. However, a large numbers of waters (up to 128 waters) are required to fully describe chemical events in the extended hydrations shells and long simulation times are needed to reliably sample the system. Taken together this makes simulation at the 1st principles level a very large computational problem. Our AIMD simulation results using these methods agree with the measured octahedral structure of the 1st solvation shell of Al3+ at the 1st shell boundary and a calculated radius of 1.937 (exp. 1.9). Our calculated average 2nd shell radius agrees remarkably well with the measured radius, 4.093 calculated vs. the measured value of 4.0-4.15 . Less can be experimentally determined about the structure of the 2nd shell. Our simulations show that this shell contains roughly 12 water molecules, which are trigonally coordinated to the 1st shell waters. This structure cannot be measured directly. However, the number of 2nd shell water molecules predicted by the simulation is consistent with experimental estimates. Tetrahedral bulk water coordination reappears just after the 2nd shell. Simulations with 128 waters are close to the maximum size that can effectively be performed with present day methods. While the time scale of our simulation are not long enough to observe transfers of waters from the 1st to the 2nd shell, we do see transfers occurring on a picosecond time scale between the 2nd shell and 3rd shell via an associative mechanism. This is faster than, but consistent with, the results of measurements on the more tightly bound Cr3+ system. For high temperature simulations, proton transfers occur in the solvation shells leading to transient hydrolysis species. The reaction coordinate for proton transfer involves the coordinates of neighboring solvent waters as in the Grotis mechanism for proton transfer in bulk water. Directly removing a proton from the hexaqua Al3+ ion leads to a much more labile solvation shell and to a five coordinated Al3+ ion. This is consistent with very recent rate measurements of ligand exchange and the conjugate base labilization effect. For the Al3+-H2O system results for high but subcritical temperatures are qualitatively similar to room temperature simulations. However, preliminary simulations for supercritical temperatures (750K) suggest that there may be a dramatic change in behavior in the hydration structure of ions for these temperatures. For transition metal ions the presence of d valence electrons plays a significant role in the behavior of the system. Our preliminary results for the Fe3+ ion suggest that this ion which is larger radius than the Al3+ ion has somewhat less rigid 1st and 2nd solvation shell. II. Gibbs Ensemble Monte Carlo Simulation of Vapor/Liquid and Metastable Liquid/Liquid Phase Equilibria in the CO2-CH4-N2 System Many fluid inclusions have compositions in the system CO2-CH4-N2. Estimates of the saturation pressures, compositions and volumetric properties of coexisting phases in the unaries, binaries and the ternary of this system have been obtained from simulations using the Gibbs Ensemble Monte Carlo method. The temperature and pressure range considered include liquid/vapor, gas/gas and metastable liquid/liquid regions. All the molecular interactions in the system were described with two-body Lennard-Jones potentials requiring only two temperature independent parameters for interactions between like molecules. The Berthhelot-Lorentz rules are used to define the Lennard-Jones interactions for unlike molecules with one additional temperature independent mixing parameter. The equilibrium compositions and molar volumes of the coexisting phases in all the mixtures are predicted with accuracy close to that of the data. These results, particularly for the phase densities and critical parameters, are considerably closer to the observed values than those that have been reported using equation of state methods(116). For very low temperatures liquid/metastable liquid/vapor coexistence was observed for the CO2-N2 and the CH4-CO2 systems, e.g. the L1L2V line. The possibility of gas-gas coexistence for the binary N2-CO2 at high temperatures and pressures was also investigated but not observed.« less

Eco-friendly synthesis of core-shell structured (TiO2/Li2CO3) nanomaterials for low cost dye-sensitized solar cells.

PubMed

Karuppuchamy, S; Brundha, C

2016-12-01

Core-shell structured TiO 2 /Li 2 CO 3 electrode was successfully synthesized by eco-friendly solution growth technique. TiO 2 /Li 2 CO 3 electrodes were characterized using X-ray Diffractometer (XRD), Scanning electron microscopy (SEM) and photocurrent-voltage measurements. The synthesized core-shell electrode material was sensitized with tetrabutylammonium cis-di(thiocyanato)-N,N'-bis(4-carboxylato-4'-carboxylic acid-2,2'-bipyridine)ruthenate(II) (N-719). The performance of dye-sensitized solar cells (DSCs) based on N719 dye modified TiO 2 /Li 2 CO 3 electrodes was investigated. The effect of various shell thickness on the photovoltaic performance of the core-shell structured electrode is also investigated. We found that Li 2 CO 3 shells of all thicknesses perform as inert barriers which improve open-circuit voltage (V oc ) of the DSCs. The energy conversion efficiency was greatly dependent on the thickness of Li 2 CO 3 on TiO 2 film, and the highest efficiency of 3.7% was achieved at the optimum Li 2 CO 3 shell layer. Copyright © 2015 Elsevier Inc. All rights reserved.

Design and Fabrication of a Ring-Stiffened Graphite-Epoxy Corrugated Cylindrical Shell

NASA Technical Reports Server (NTRS)

Johnson, R., Jr.

1978-01-01

Design and fabrication of supplement test panels that represent key portions of the cylinder are described, as are supporting tests of coupons, sample joints, and stiffening ring elements. The cylindrical shell is a ring-stiffened, open corrugation design that uses T300/5208 graphite-epoxy tape as the basic material for the shell wall and stiffening rings. The test cylinder is designed to withstand bending loads producing the relatively low maximum load intensity in the shell wall of 1,576 N/cm. The resulting shell wall weight, including stiffening rings and fasteners, is 0.0156 kg/m. The shell weight achieved in the graphite-epoxy cylinder represents a weight saving of approximately 23 percent, compared to a comparable aluminum shell. A unique fabrication approach was used in which the cylinder wall was built in three flat segments, which were then wrapped to the cylindrical shape. Such an approach, made possible by the flexibility of the thin corrugated wall in a radial direction, proved to be a simple approach to building the test cylinder. Based on tooling and fabrication methods in this program, the projected costs of a production run of 100 units are reported.

Thesis - keeping the management system {open_quotes}live{close_quotes} and reaching the workforce

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

Primrose, M.J.; Bentley, P.D.; Graaf, G.C. van der

1996-12-31

Previous papers given to SPE conferences have described the Shell Group approach to Safety Management Systems and to Safety Cases. Their extension to HSE MS and to HSE Cases has also been addressed. Since 1984 the Enhanced Safety Management (ESM) programme within Shell companies has led to a significant improvement in the management of safety but it was only when structured management systems (based upon an understanding of the business processes) were introduced that true integration of HSE as a line responsibility became a reality. This paper describes the THESIS software package and the way that management systems have beenmore » made {open_quote}live{close_quote} and how workforce involvement can be demonstrated.« less

A revised MRCI-algorithm. I. Efficient combination of spin adaptation with individual configuration selection coupled to an effective valence-shell Hamiltonian

NASA Astrophysics Data System (ADS)

Strodel, Paul; Tavan, Paul

2002-09-01

We present a revised multi-reference configuration interaction (MRCI) algorithm for balanced and efficient calculation of electronic excitations in molecules. The revision takes up an earlier method, which had been designed for flexible, state-specific, and individual selection (IS) of MRCI expansions, included perturbational corrections (PERT), and used the spin-coupled hole-particle formalism of Tavan and Schulten (1980) for matrix-element evaluation. It removes the deficiencies of this method by introducing tree structures, which code the CI bases and allow us to efficiently exploit the sparseness of the Hamiltonian matrices. The algorithmic complexity is shown to be optimal for IS/MRCI applications. The revised IS/MRCI/PERT module is combined with the effective valence shell Hamiltonian OM2 suggested by Weber and Thiel (2000). This coupling serves the purpose of making excited state surfaces of organic dye molecules accessible to relatively cheap and sufficiently precise descriptions.

Optimization of Biosorptive Removal of Dye from Aqueous System by Cone Shell of Calabrian Pine

PubMed Central

Deniz, Fatih

2014-01-01

The biosorption performance of raw cone shell of Calabrian pine for C.I. Basic Red 46 as a model azo dye from aqueous system was optimized using Taguchi experimental design methodology. L9 (33) orthogonal array was used to optimize the dye biosorption by the pine cone shell. The selected factors and their levels were biosorbent particle size, dye concentration, and contact time. The predicted dye biosorption capacity for the pine cone shell from Taguchi design was obtained as 71.770 mg g−1 under optimized biosorption conditions. This experimental design provided reasonable predictive performance of dye biosorption by the biosorbent (R 2: 0.9961). Langmuir model fitted better to the biosorption equilibrium data than Freundlich model. This displayed the monolayer coverage of dye molecules on the biosorbent surface. Dubinin-Radushkevich model and the standard Gibbs free energy change proposed physical biosorption for predominant mechanism. The logistic function presented the best fit to the data of biosorption kinetics. The kinetic parameters reflecting biosorption performance were also evaluated. The optimization study revealed that the pine cone shell can be an effective and economically feasible biosorbent for the removal of dye. PMID:25405213

Composites Based on Core-Shell Structured HBCuPc@CNTs-Fe3O4 and Polyarylene Ether Nitriles with Excellent Dielectric and Mechanical Properties

NASA Astrophysics Data System (ADS)

Pu, Zejun; Zhong, Jiachun; Liu, Xiaobo

2017-10-01

Core-shell structured magnetic carbon nanotubes (CNTs-Fe3O4) coated with hyperbranched copper phthalocyanine (HBCuPc) (HBCuPc@CNTs-Fe3O4) hybrids were prepared by the solvent-thermal method. The results indicated that the HBCuPc molecules were decorated on the surface of CNTs-Fe3O4 through coordination behavior of phthalocyanines, and the CNTs-Fe3O4 core was completely coaxial wrapped by a functional intermediate HBCuPc shell. Then, polymer-based composites with a relatively high dielectric constant and low dielectric loss were fabricated by using core-shell structured HBCuPc@CNTs-Fe3O4 hybrids as fillers and polyarylene ether nitriles (PEN) as the polymer matrix. The cross-sectional scanning electron microscopy (SEM) images of composites showed that there is almost no agglomeration and internal delamination. In addition, the rheological analysis reveals that the core-shell structured HBCuPc@CNTs-Fe3O4 hybrids present better dispersion and stronger interface adhesion with the PEN matrix than CNTs-Fe3O4, thus resulting in significant improvement of the mechanical, thermal and dielectric properties of polymer-based composites.

New insights into the photocatalytic activity of 3-D core-shell P25@silica nanocomposites: impact of mesoporous coating.

PubMed

Gong, Yichao; Wang, Dan Ping; Wu, Renbing; Gazi, Sarifuddin; Soo, Han Sen; Sritharan, Thirumany; Chen, Zhong

2017-04-11

In this report, a three-dimensional (3-D) network of core-shell TiO 2 (P25)-mesoporous SiO 2 (P25@mSiO 2 ) nanocomposites was prepared via a controllable surfactant-assisted sol-gel method. The nanocomposites were investigated for photocatalytic reactions of organic dye degradation, water splitting, and CO 2 reduction to understand the roles of the mSiO 2 shell in these photocatalytic reactions. It was found that the mSiO 2 shell accelerates the photodegradation of the organic dye, but dramatically reduces the photocatalytic activity of P25 in water splitting and CO 2 reduction. The roles played by the mSiO 2 shell in the photocatalytic reactions are summarized as: (1) effective prevention of agglomeration of P25 nanoparticles, (2) facilitating the transfer of uncharged photo-generated ˙OH radicals via the abundant -OH groups on the mesoporous surface, (3) provision of increased reaction sites between ˙OH radicals and dye molecules by its mesoporous nanostructure and large surface area, and (4) prevention of diffusion of the photo-generated charge carriers (photoelectrons and photoholes) because of its insulating nature.

Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

NASA Astrophysics Data System (ADS)

Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane

2017-04-01

Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of the studied deposits, no evidence for significant riverine influence on the strontium-isotope signature is observed. The new chemostratigraphic data will provide a more precise age assignment for Kimmeridgian strata in the Lower Saxony Basin and thus enable the establishment of a solid integrated stratigraphic scheme that can be used for correlation on both regional and global scale.

Design and fabrication of memory devices based on nanoscale polyoxometalate clusters

NASA Astrophysics Data System (ADS)

Busche, Christoph; Vilà-Nadal, Laia; Yan, Jun; Miras, Haralampos N.; Long, De-Liang; Georgiev, Vihar P.; Asenov, Asen; Pedersen, Rasmus H.; Gadegaard, Nikolaj; Mirza, Muhammad M.; Paul, Douglas J.; Poblet, Josep M.; Cronin, Leroy

2014-11-01

Flash memory devices--that is, non-volatile computer storage media that can be electrically erased and reprogrammed--are vital for portable electronics, but the scaling down of metal-oxide-semiconductor (MOS) flash memory to sizes of below ten nanometres per data cell presents challenges. Molecules have been proposed to replace MOS flash memory, but they suffer from low electrical conductivity, high resistance, low device yield, and finite thermal stability, limiting their integration into current MOS technologies. Although great advances have been made in the pursuit of molecule-based flash memory, there are a number of significant barriers to the realization of devices using conventional MOS technologies. Here we show that core-shell polyoxometalate (POM) molecules can act as candidate storage nodes for MOS flash memory. Realistic, industry-standard device simulations validate our approach at the nanometre scale, where the device performance is determined mainly by the number of molecules in the storage media and not by their position. To exploit the nature of the core-shell POM clusters, we show, at both the molecular and device level, that embedding [(Se(IV)O3)2]4- as an oxidizable dopant in the cluster core allows the oxidation of the molecule to a [Se(V)2O6]2- moiety containing a {Se(V)-Se(V)} bond (where curly brackets indicate a moiety, not a molecule) and reveals a new 5+ oxidation state for selenium. This new oxidation state can be observed at the device level, resulting in a new type of memory, which we call `write-once-erase'. Taken together, these results show that POMs have the potential to be used as a realistic nanoscale flash memory. Also, the configuration of the doped POM core may lead to new types of electrical behaviour. This work suggests a route to the practical integration of configurable molecules in MOS technologies as the lithographic scales approach the molecular limit.

OpenSim: A Flexible Distributed Neural Network Simulator with Automatic Interactive Graphics.

PubMed

Jarosch, Andreas; Leber, Jean Francois

1997-06-01

An object-oriented simulator called OpenSim is presented that achieves a high degree of flexibility by relying on a small set of building blocks. The state variables and algorithms put in this framework can easily be accessed through a command shell. This allows one to distribute a large-scale simulation over several workstations and to generate the interactive graphics automatically. OpenSim opens new possibilities for cooperation among Neural Network researchers. Copyright 1997 Elsevier Science Ltd.

Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

NASA Astrophysics Data System (ADS)

Aleksandrova, E. O.; Novichkov, R. V.; Olenin, A. Yu.; Zuev, B. K.

2017-03-01

Silica nanoparticles are obtained according to the Stober-Fink-Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50-200 nm) form during primary chemical process; the average size of the particles can be increased to 400-500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

The chemical composition of the egg shells of the potato cyst-nematode, Heterodera rostochiensis Woll

PubMed Central

Clarke, A. J.; Cox, Patricia M.; Shepherd, Audrey M.

1967-01-01

1. Eggs of the potato cyst-nematode (Heterodera rostochiensis Woll.) were isolated by sieving a suspension of crushed cysts. Eggs were broken open by ultrasonic vibration and the egg shells separated from the released larvae by centrifuging in a potassium tartrate density gradient. About 1 mg. of dried egg shells was obtained from 1000 cysts. 2. The major constituent of the egg shells was protein (59%, calculated from nitrogen content). About 80% of the egg shells went into solution on acid hydrolysis. Of the 18 amino acids determined with the Technicon Auto-Analyser, proline was most abundant and, with aspartic acid, glycine and serine, made up about 64% by weight of the total amino acids. The small amounts of aromatic and sulphur-containing amino acids, and the presence of hydroxy-proline, indicate a collagen-like protein. 3. The egg shells gave a positive van Wisselingh colour test for chitin, and glucosamine was detected in their acid hydrolysate by chromatography. The glucosamine content of the egg shells, determined by the Elson–Morgan colorimetric method, was 7%, corresponding to about 9% chitin. 4. Dried egg shells contained about 7% of lipid, 6% of carbohydrate and 3% of ash. Polyphenols (3% by weight of the egg shells) were detected in the acid hydrolysates. 5. Neither the collagen nor the chitin showed evidence of crystallinity when examined by X-ray diffraction. PMID:6069200

Dye-sensitized solar cells employing a SnO2-TiO2 core-shell structure made by atomic layer deposition.

PubMed

Karlsson, Martin; Jõgi, Indrek; Eriksson, Susanna K; Rensmo, Håkan; Boman, Mats; Boschloo, Gerrit; Hagfeldt, Anders

2013-01-01

This paper describes the synthesis and characterization of core-shell structures, based on SnO2 and TiO2, for use in dye-sensitized solar cells (DSC). Atomic layer deposition is employed to control and vary the thickness of the TiO2 shell. Increasing the TiO2 shell thickness to 2 nm improved the device performance of liquid electrolyte-based DSC from 0.7% to 3.5%. The increase in efficiency originates from a higher open-circuit potential and a higher short-circuit current, as well as from an improvement in the electron lifetime. SnO2-TiO2 core-shell DSC devices retain their photovoltage in darkness for longer than 500 seconds, demonstrating that the electrons are contained in the core material. Finally core-shell structures were used for solid-state DSC applications using the hole transporting material 2,2',7,7',-tetrakis(N, N-di-p-methoxyphenyl-amine)-9,9',-spirofluorene. Similar improvements in device performance were obtained for solid-state DSC devices.

The geometry of protein hydration

NASA Astrophysics Data System (ADS)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Based on molecular dynamics simulations of four globular proteins in dilute aqueous solution, with three different water models, we examine several, essentially geometrical, aspects of the protein-water interface that remain controversial or incompletely understood. First, we compare different hydration shell definitions, based on spatial or topological proximity criteria. We find that the best method for constructing monolayer shells with nearly complete coverage is to use a 5 Å water-carbon cutoff and a 4 Å water-water cutoff. Using this method, we determine a mean interfacial water area of 11.1 Å2 which appears to be a universal property of the protein-water interface. We then analyze the local coordination and packing density of water molecules in the hydration shells and in subsets of the first shell. The mean polar water coordination number in the first shell remains within 1% of the bulk-water value, and it is 5% lower in the nonpolar part of the first shell. The local packing density is obtained from additively weighted Voronoi tessellation, arguably the most physically realistic method for allocating space between protein and water. We find that water in all parts of the first hydration shell, including the nonpolar part, is more densely packed than in the bulk, with a shell-averaged density excess of 6% for all four proteins. We suggest reasons why this value differs from previous experimental and computational results, emphasizing the importance of a realistic placement of the protein-water dividing surface and the distinction between spatial correlation and packing density. The protein-induced perturbation of water coordination and packing density is found to be short-ranged, with an exponential decay "length" of 0.6 shells. We also compute the protein partial volume, analyze its decomposition, and argue against the relevance of electrostriction.

Control Strategies for Zebra Mussel Infestations at Public Facilities

DTIC Science & Technology

1992-07-01

detailed examina- tion of hard -to-reach surfaces or specific components (such as fire protection systems or intake pipes for sensor devices) should...trash racks. Trash racks could become partially clogged with zebra mussels, shells , and other debris. Flow through the openings would be reduced, and... shells to the top of the lock wall. These are now used by Ontario Hydro for removing zebra mussels. At most facilities, the culvert is totally dewatered

Ray Solutions to Sound Scattering by Complex Bodies: Application to Zooplankton.

DTIC Science & Technology

2000-02-14

marine snail that swims (elastic shelled body), and (c) siphonophore , a gas- bearing animal (fluid-like tissue containing gas). From Ref. 1...1- LU -100 ^/Vyvv -100 EUPHAUSIID GASTROPOD SIPHONOPHORE 400 500 600 700 800 400 500 600 700 800 FREQUENCY (kHz) FIGURE 2 Target...whose bodies consist of an irregular elastic shell with an opening, and a siphonophore whose body is mostly a fluid-like tissue that contains a

Temporal and local variations in biochemical composition of Crassostrea gigas shells

NASA Astrophysics Data System (ADS)

Almeida, Maria J.; Machado, Jorge; Moura, Gabriela; Azevedo, Manuela; Coimbra, João

1998-12-01

The objective of this work was to find relations between organic and inorganic shell components. Crassostrea gigas shells were analysed from live specimens collected at five different stations: the Lima estuary (1), the Ria de Aveiro (2, 3), and the Mondego estuary (4, 5), Portugal. About 30% of the oysters, from stations 1, 2 and 3 had shell-thickness-index values ≤10, indicating a severe thickening. Oysters from the Mondego estuary contained mud blisters due to Polydora infestations. Oysters from station 3 had thicker shells and showed a higher Pb content in shell and tissues than oysters from the other stations. Amino-acid composition changed mainly according to the modified protein (jelly-like substance) probably produced by the presence of TBT (tributyltin) in the water; in particular, we observed an increase in glutamic acid and threonine and a decrease in major amino acids such as aspartic acid, serine and glycine. Elemental shell composition was mainly associated with environmental conditions: shells from stations in open areas had higher Li, Cd, Cr and Ca and lower Mn levels than those from semi-enclosed areas (fish farms). Discriminant analyses against the three kinds of shell observed (normal, thick and infested), using chemical elements and amino acids as discriminant variables, showed the infested group to have the biggest differences. There was no correlation between amino-acid and chemical-element patterns in shell composition. Observed changes in amino-acid pattern, probably due to TBT, did not imply a simultaneous change of elemental composition.

Structure and properties of silk from the African wild silkmoth Gonometa postica reared indoors

PubMed Central

Teshome, Addis; Raina, S. K.; Vollrath, Fritz

2014-01-01

Abstract African wild silkmoth, Gonometa postica Walker (Lepidoptera: Lasiocampidae), were reared indoors in order to examine the influence of rearing conditions on the structure and properties of silk cocoon shells and degummed fibers by using a scanning electron microscope, an Instron tensile tester, and a thermogravimetric analyzer. The cocoons reared indoors showed inferior quality in weight, length, width, and cocoon shell ratio compared to cocoons reared outdoors. There were no differences in cocoon shell and fiber surfaces and cross sectional structures. Cocoon shells were covered with calcium oxalate crystals with few visible fibers on their surface. Degummed fibers were smooth with minimum unfractured surfaces and globular to triangular cross sections. Indoor-reared cocoon shells had a significantly higher breaking strain, while the breaking stress was higher for cocoons reared outdoors. Fibers from indoor cocoons had a significantly higher breaking stress while outdoor fibers had higher breaking strain. Thermogravimetric analysis curves showed two main thermal reactions revealing the dehydration of water molecules and ir-reversible decomposition of the crystallites in both cocoons and fibers reared indoors and outdoors. Cocoon shells underwent additional peaks of decomposition with increased temperature. The total weight loss was higher for cocoon shells and degummed fibers from indoors. Rearing conditions (temperature and relative humidity), feeding method used, changes in total life span, days to molting, and spinning might have influenced the variation in the properties observed.The ecological and commercial significances of indoor rearing of G. postica are discussed. PMID:25373183

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

NASA Astrophysics Data System (ADS)

Linkov, P. A.; Vokhmintcev, K. V.; Samokhvalov, P. S.; Laronze-Cochard, M.; Sapi, J.; Nabiev, I. R.

2018-02-01

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.

On the intermolecular vibrational coupling, hydrogen bonding, and librational freedom of water in the hydration shell of mono- and bivalent anions.

PubMed

Ahmed, Mohammed; Namboodiri, V; Singh, Ajay K; Mondal, Jahur A

2014-10-28

The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.

Controllable synthesis of ZnxCd1-xS@ZnO core-shell nanorods with enhanced photocatalytic activity.

PubMed

Xie, Shilei; Lu, Xihong; Zhai, Teng; Gan, Jiayong; Li, Wei; Xu, Ming; Yu, Minghao; Zhang, Yuan-Ming; Tong, Yexiang

2012-07-17

We report the synthesis of Zn(x)Cd(1-x)S@ZnO nanorod arrays via a facile two-step process and the implementation of these core-shell nanorods as an environmental friendly and recyclable photocatalyst for methyl orange degradation. The band gap of Zn(x)Cd(1-x)S@ZnO core-shell nanorods can be readily tunable by adjusting the ratio of Zn/Cd during the synthesis. These Zn(x)Cd(1-x)S@ZnO core-shell nanorods exhibit a high photocatalytic activity and good stability in the degradation of the methyl orange. Moreover, these films grown on FTO substrates make the collection and recycle of the photocatalyst easier. These findings may open new opportunities for the design of effective, stable, and easy-recyclable photocatalytic materials.

Processes in suspensions of nanocomposite microcapsules exposed to external electric fields

NASA Astrophysics Data System (ADS)

Ermakov, A. V.; Lomova, M. V.; Kim, V. P.; Chumakov, A. S.; Gorbachev, I. A.; Gorin, D. A.; Glukhovskoy, E. G.

2016-04-01

Microcapsules with and without magnetite nanoparticles incorporated in the polyelectrolyte shell were prepared. The effect of external electric field on the nanocomposite polyelectrolyte microcapsules containing magnetite nanoparticles in the shell was studied in this work as a function of the electric field strength. Effect of electric fields on polyelectrolyte microcapsules and the control over integrity of polyelectrolyte microcapsules with and without inorganic nanoparticles by constant electric field has been investigated. Beads effect, aggregation and deformations of nanocomposite microcapsule shell in response to electric field were observed by confocal laser scanning microscopy (CLSM). Thus, a new approach for effect on the nanocomposite microcapsule, including opening microcapsule shell by an electric field, was demonstrated. These results can be used for creation of new systems for drug delivery systems with controllable release by external electric field.

Bioactive compounds in cashew nut (Anacardium occidentale L.) kernels: effect of different shelling methods.

PubMed

Trox, Jennifer; Vadivel, Vellingiri; Vetter, Walter; Stuetz, Wolfgang; Scherbaum, Veronika; Gola, Ute; Nohr, Donatus; Biesalski, Hans Konrad

2010-05-12

In the present study, the effects of various conventional shelling methods (oil-bath roasting, direct steam roasting, drying, and open pan roasting) as well as a novel "Flores" hand-cracking method on the levels of bioactive compounds of cashew nut kernels were investigated. The raw cashew nut kernels were found to possess appreciable levels of certain bioactive compounds such as beta-carotene (9.57 microg/100 g of DM), lutein (30.29 microg/100 g of DM), zeaxanthin (0.56 microg/100 g of DM), alpha-tocopherol (0.29 mg/100 g of DM), gamma-tocopherol (1.10 mg/100 g of DM), thiamin (1.08 mg/100 g of DM), stearic acid (4.96 g/100 g of DM), oleic acid (21.87 g/100 g of DM), and linoleic acid (5.55 g/100 g of DM). All of the conventional shelling methods including oil-bath roasting, steam roasting, drying, and open pan roasting revealed a significant reduction, whereas the Flores hand-cracking method exhibited similar levels of carotenoids, thiamin, and unsaturated fatty acids in cashew nuts when compared to raw unprocessed samples.

Block coordination copolymers

DOEpatents

Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

2014-11-11

The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

Block coordination copolymers

DOEpatents

Koh, Kyoung Moo; Wong-Foy, Antek G.; Matzger, Adam J.; Benin, Annabelle I.; Willis, Richard R.

2012-12-04

The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

Block coordination copolymers

DOEpatents

Koh, Kyoung Moo; Wong-Foy, Antek G; Matzger, Adam J; Benin, Annabelle I; Willis, Richard R

2012-11-13

The present invention provides compositions of crystalline coordination copolymers wherein multiple organic molecules are assembled to produce porous framework materials with layered or core-shell structures. These materials are synthesized by sequential growth techniques such as the seed growth technique. In addition, the invention provides a simple procedure for controlling functionality.

A thermoresponsive nanorattle containing two different catalysts for controllable one-pot tandem catalysis

NASA Astrophysics Data System (ADS)

Niu, Chengrong; Hu, Jie; Li, Yinfeng; Leng, Jinghang; Li, Songjun

2018-03-01

In the present work, a thermoresponsive nanorattle with a Ag nanoparticle (NP) core (one catalyst in the nanorattle), and a poly(N-isopropylacrylamide) shell was developed. An imidazole group was grafted on the polymer shell by copolymerization as the other catalyst. Owing to the catalytic activities of the imidazole group and Ag NP with regards to hydrolysis and reduction, respectively, this nanorattle exhibited tandem-reaction catalytic abilities. In addition, because of the shrinkage of the poly(N-isopropylacrylamide) shell at high temperatures, the tandem reaction could be controlled to stop at the first reaction step. That is to say, only the hydrolysis reaction was catalyzed by the imidazole group being grafted on the surface of the shell. The reduction step in the tandem reaction catalyzed by the Ag particle, however, was switched off by the shrinkage of the poly(N-isopropylacrylamide) shell. This protocol opens up an opportunity to develop controllable catalysts for complicated chemical processes.

A platonic solid templating Archimedean solid: an unprecedented nanometre-sized Ag37 cluster

NASA Astrophysics Data System (ADS)

Li, Xiao-Yu; Su, Hai-Feng; Yu, Kai; Tan, Yuan-Zhi; Wang, Xing-Po; Zhao, Ya-Qin; Sun, Di; Zheng, Lan-Sun

2015-04-01

The spontaneous formation of discrete spherical nanosized molecules is prevalent in nature, but the authentic structural mimicry of such highly symmetric polyhedra from edge sharing of regular polygons has remained elusive. Here we present a novel ball-shaped {(HNEt3)[Ag37S4(SC6H4tBu)24(CF3COO)6(H2O)12]} cluster (1) that is assembled via a one-pot process from polymeric {(HNEt3)2[Ag10(SC6H4tBu)12]}n and CF3COOAg. Single crystal X-ray analysis confirmed that 1 is a Td symmetric spherical molecule with a [Ag36(SC6H4tBu)24] anion shell enwrapping a AgS4 tetrahedron. The shell topology of 1 belongs to one of 13 Archimedean solids, a truncated tetrahedron with four edge-shared hexagons and trigons, which are supported by a AgS4 Platonic solid in the core. Interestingly, the cluster emits green luminescence centered at 515 nm at room temperature. Our investigations have provided a promising synthetic protocol for a high-nuclearity silver cluster based on underlying geometrical principles.The spontaneous formation of discrete spherical nanosized molecules is prevalent in nature, but the authentic structural mimicry of such highly symmetric polyhedra from edge sharing of regular polygons has remained elusive. Here we present a novel ball-shaped {(HNEt3)[Ag37S4(SC6H4tBu)24(CF3COO)6(H2O)12]} cluster (1) that is assembled via a one-pot process from polymeric {(HNEt3)2[Ag10(SC6H4tBu)12]}n and CF3COOAg. Single crystal X-ray analysis confirmed that 1 is a Td symmetric spherical molecule with a [Ag36(SC6H4tBu)24] anion shell enwrapping a AgS4 tetrahedron. The shell topology of 1 belongs to one of 13 Archimedean solids, a truncated tetrahedron with four edge-shared hexagons and trigons, which are supported by a AgS4 Platonic solid in the core. Interestingly, the cluster emits green luminescence centered at 515 nm at room temperature. Our investigations have provided a promising synthetic protocol for a high-nuclearity silver cluster based on underlying geometrical principles. Electronic supplementary information (ESI) available: detailed synthesis procedure, tables, crystal data in CIF files, IR data, TGA results and powder X-ray diffractogram for 1. CCDC 1042228. See DOI: 10.1039/c5nr01222h

Direct photoassociation of halo molecules in ultracold 86 Sr

NASA Astrophysics Data System (ADS)

Aman, J. A.; Hill, Joshua; Killian, T. C.

2017-04-01

We investigate the creation of 1S0 +1S0 halo molecules in strontium 86 through direct photoassociation in an optical dipole trap. We drive two photon Raman transitions near-resonance with a molecular level of the 1S0 +3P1 interatomic potential as the intermediate state. This provides large Frank-Condon factors and allows us to observe resonances for the creation of halo molecules through higher order Raman processes. The halo molecule is bound by EB 85 kHz at low excitation-laser intensity, but experiments show large AC Stark shifts of the molecular binding energy. These conditions suggest that STIRAP should be very effective for improving molecular conversion efficiency. Further experiments in a 3D lattice will explore molecular lifetimes and collision rates. Travel support provided by Shell Corporation.

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

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

Mei, Yuan; Liu, Weihua; Migdiov, A. A.

We invesmore » tigated the hydration of the CuCl 0 complex in HCl-bearing water vapor at 350°C and a vapor-like fluid density between 0.02 and 0.09 g/cm 3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H 2O-Cu-Cl] 0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ~0.5 to ~3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm 3 ( f H 2O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal “vapors” in the experiments. Finally, our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.« less

CuCl Complexation in the Vapor Phase: Insights from Ab Initio Molecular Dynamics Simulations

DOE PAGES

Mei, Yuan; Liu, Weihua; Migdiov, A. A.; ...

2018-05-02

We invesmore » tigated the hydration of the CuCl 0 complex in HCl-bearing water vapor at 350°C and a vapor-like fluid density between 0.02 and 0.09 g/cm 3 using ab initio molecular dynamics (MD) simulations. The simulations reveal that one water molecule is strongly bonded to Cu(I) (first coordination shell), forming a linear [H 2O-Cu-Cl] 0 moiety. The second hydration shell is highly dynamic in nature, and individual configurations have short life-spans in such low-density vapors, resulting in large fluctuations in instantaneous hydration numbers over a timescale of picoseconds. The average hydration number in the second shell (m) increased from ~0.5 to ~3.5 and the calculated number of hydrogen bonds per water molecule increased from 0.09 to 0.25 when fluid density (which is correlated to water activity) increased from 0.02 to 0.09 g/cm 3 ( f H 2O 1.72 to 2.05). These changes of hydration number are qualitatively consistent with previous solubility studies under similar conditions, although the absolute hydration numbers from MD were much lower than the values inferred by correlating experimental Cu fugacity with water fugacity. This could be due to the uncertainties in the MD simulations and uncertainty in the estimation of the fugacity coefficients for these highly nonideal “vapors” in the experiments. Finally, our study provides the first theoretical confirmation that beyond-first-shell hydrated metal complexes play an important role in metal transport in low-density hydrothermal fluids, even if it is highly disordered and dynamic in nature.« less

The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core.

PubMed

Jiménez-Serra, Izaskun; Vasyunin, Anton I; Caselli, Paola; Marcelino, Nuria; Billot, Nicolas; Viti, Serena; Testi, Leonardo; Vastel, Charlotte; Lefloch, Bertrand; Bachiller, Rafael

2016-10-10

The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with A V ≥30 mag within the inner 2700 au; and a low-density shell with average A V ~7.5-8 mag located at 4000 au from the core's center and bright in CH 3 OH. Our observations show that CH 3 O, CH 3 OCH 3 and CH 3 CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH 3 OCHO, c-C 3 H 2 O, HCCCHO, CH 2 CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains.

The Spatial Distribution of Complex Organic Molecules in the L1544 Pre-stellar Core

PubMed Central

Jiménez-Serra, Izaskun; Vasyunin, Anton I.; Caselli, Paola; Marcelino, Nuria; Billot, Nicolas; Viti, Serena; Testi, Leonardo; Vastel, Charlotte; Lefloch, Bertrand; Bachiller, Rafael

2016-01-01

The detection of complex organic molecules (COMs) toward cold sources such as pre-stellar cores (with T<10 K), has challenged our understanding of the formation processes of COMs in the interstellar medium. Recent modelling on COM chemistry at low temperatures has provided new insight into these processes predicting that COM formation depends strongly on parameters such as visual extinction and the level of CO freeze out. We report deep observations of COMs toward two positions in the L1544 pre-stellar core: the dense, highly-extinguished continuum peak with AV ≥30 mag within the inner 2700 au; and a low-density shell with average AV ~7.5-8 mag located at 4000 au from the core’s center and bright in CH3OH. Our observations show that CH3O, CH3OCH3 and CH3CHO are more abundant (by factors ~2-10) toward the low-density shell than toward the continuum peak. Other COMs such as CH3OCHO, c-C3H2O, HCCCHO, CH2CHCN and HCCNC show slight enhancements (by factors ≤3) but the associated uncertainties are large. This suggests that COMs are actively formed and already present in the low-density shells of pre-stellar cores. The modelling of the chemistry of O-bearing COMs in L1544 indicates that these species are enhanced in this shell because i) CO starts freezing out onto dust grains driving an active surface chemistry; ii) the visual extinction is sufficiently high to prevent the UV photo-dissociation of COMs by the external interstellar radiation field; and iii) the density is still moderate to prevent severe depletion of COMs onto grains. PMID:27733899

Preparation of keratin-based microcapsules for encapsulation of hydrophilic molecules.

PubMed

Rajabinejad, Hossein; Patrucco, Alessia; Caringella, Rosalinda; Montarsolo, Alessio; Zoccola, Marina; Pozzo, Pier Davide

2018-01-01

The interest towards microcapsules based on non-toxic, biodegradable and biocompatible polymers, such as proteins, is increasing considerably. In this work, microcapsules were prepared using water soluble keratin, known as keratoses, with the aim of encapsulating hydrophilic molecules. Keratoses were obtained via oxidizing extraction of pristine wool, previously degreased by Soxhlet. In order to better understand the shell part of microcapsules, pristine wool and obtained keratoses were investigated by FT-IR, gel-electrophoresis and HPLC. Production of the microcapsules was carried out by a sonication method. Thermal properties of microcapsules were investigated by DSC. Microencapsulation and dye encapsulation yields were obtained by UV-spectroscopy. Morphological structure of microcapsules was studied by light microscopy, SEM, and AFM. The molecular weights of proteins analyzed using gel-electrophoresis resulted in the range of 38-62kDa. The results confirmed that the hydrophilic dye (Telon Blue) was introduced inside the keratoses shells by sonication and the final microcapsules diameter ranged from 0.5 to 4µm. Light microscope investigation evidenced the presence of the dye inside the keratoses vesicles, confirming their capability of encapsulating hydrophilic molecules. The microcapsule yield and dye encapsulation yield were found to be 28.87±3% and 83.62±5% respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

Latex imaging by environmental STEM: application to the study of the surfactant outcome in hybrid alkyd/acrylate systems.

PubMed

Faucheu, Jenny; Chazeau, Laurent; Gauthier, Catherine; Cavaillé, Jean-Yves; Goikoetxea, Monika; Minari, Roque; Asua, José M

2009-09-01

Among other uses, latexes are a successful alternative to solvent-borne binders for coatings. Efforts are made to produce hybrid nanostructured latexes containing an acrylic phase and an alkyd phase. However, after the film-forming process, the surfactant used to stabilize these latexes remains in the film, and its location can have a drastic effect on the application properties. Among the processing parameters, the alkyd hydrophobicity can strongly influence this location. This article aims at the imaging of these surfactant molecules in two hybrid latexes with different hydrophobicity level of the alkyd resin. A first part of this paper is dedicated to the understanding of the contrast provided by the surfactant in environmental STEM imaging of latexes. Then, the influence of surfactant-polymer affinity on the surfactant location after film-forming of those hybrid alkyd/acrylate latexes is studied by this technique. It is shown that in the hybrid latex with an alkyd shell (obtained with the most hydrophilic resin), the surfactant molecules tend to remain buried in the alkyd phase. Conversely, in the hybrid latex with an acrylate shell (in the case of the most hydrophobic resin), the surfactant molecules tend to gather into islands like in pure acrylate latex films.

Confocal Raman microscopy as a tool to describe different mineral and organic phases at high spatial resolution within marine biogenic carbonates: case study on Nerita undata (Gastropoda, Neritopsina)

NASA Astrophysics Data System (ADS)

Nehrke, G.; Nouet, J.

2011-06-01

Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusk shells) represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (∼300 nm). Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystallographic lattice.

The Morphology of Emulsion Polymerized Latex Particles

DOE R&D Accomplishments Database

Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

1987-11-01

Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M < 10{sup 6} g/mol SANS gave zero angle scattering intensities much higher than expected on the basis of a random distribution of labeled molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

On the formation of molecules and solid-state compounds from the AGB to the PN phases

NASA Astrophysics Data System (ADS)

García-Hernández, D. A.; Manchado, A.

2016-07-01

During the asymptoyic giant branch (AGB) phase, different elements are dredge- up to the stellar surface depending on progenitor mass and metallicity. When the mass loss increases at the end of the AGB, a circumstellar dust shell is formed, where different (C-rich or O-rich) molecules and solid-state compounds are formed. These are further processed in the transition phase between AGB stars and planetary nebulae (PNe) to create more complex organic molecules and inorganic solid-state compounds (e.g., polycyclic aromatic hydrocarbons, fullerenes, and graphene precursors in C-rich environments and oxides and crystalline silicates in O-rich ones). We present an observational review of the different molecules and solid-state materials that are formed from the AGB to the PN phases. We focus on the formation routes of complex fullerene (and fullerene-based) molecules as well as on the level of dust processing depending on metallicity.

Zirconium(IV) oxide: New coating material for nanoresonators for shell-isolated nanoparticle-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Abdulrahman, Heman Burhanalden; Kołątaj, Karol; Kudelski, Andrzej

2018-03-01

One tool that can be used for determining the structure and composition of surfaces of various materials (even in in situ conditions) is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In SHINERS measurements, the surface under investigation is covered with a layer of surface-protected plasmonic nanoparticles, and then the Raman spectrum of the surface analysed is recorded. The plasmonic cores of the used core-shell structures act as electromagnetic nanoresonators, significantly locally enhancing the intensity of the electric field of the incident radiation, leading to a large increase in the efficiency of the generation of the Raman signal from molecules in the close proximity to the deposited SHINERS nanoresonators. A protective layer (from transparent dielectrics such as SiO2, Al2O3 or TiO2) prevents direct interaction between the plasmonic metal and the analysed surface (such interactions may lead to changes in the structure of the surface) and, in the case of plasmonic cores other than gold cores, the dielectric layer increases the chemical stability of the metal core. In this contribution, we show for the first time that core-shell nanoparticles having a silver core (both a solid and hollow one) and a shell of zirconium(IV) oxide are very efficient SHINERS nanoresonators that are significantly more stable in acidic and alkaline media than the silver-silica core-shell structures typically used for SHINERS experiments.

Evaluation of Kirkwood-Buff integrals via finite size scaling: a large scale molecular dynamics study

NASA Astrophysics Data System (ADS)

Dednam, W.; Botha, A. E.

2015-01-01

Solvation of bio-molecules in water is severely affected by the presence of co-solvent within the hydration shell of the solute structure. Furthermore, since solute molecules can range from small molecules, such as methane, to very large protein structures, it is imperative to understand the detailed structure-function relationship on the microscopic level. For example, it is useful know the conformational transitions that occur in protein structures. Although such an understanding can be obtained through large-scale molecular dynamic simulations, it is often the case that such simulations would require excessively large simulation times. In this context, Kirkwood-Buff theory, which connects the microscopic pair-wise molecular distributions to global thermodynamic properties, together with the recently developed technique, called finite size scaling, may provide a better method to reduce system sizes, and hence also the computational times. In this paper, we present molecular dynamics trial simulations of biologically relevant low-concentration solvents, solvated by aqueous co-solvent solutions. In particular we compare two different methods of calculating the relevant Kirkwood-Buff integrals. The first (traditional) method computes running integrals over the radial distribution functions, which must be obtained from large system-size NVT or NpT simulations. The second, newer method, employs finite size scaling to obtain the Kirkwood-Buff integrals directly by counting the particle number fluctuations in small, open sub-volumes embedded within a larger reservoir that can be well approximated by a much smaller simulation cell. In agreement with previous studies, which made a similar comparison for aqueous co-solvent solutions, without the additional solvent, we conclude that the finite size scaling method is also applicable to the present case, since it can produce computationally more efficient results which are equivalent to the more costly radial distribution function method.

Microwave and millimeter wave astrochemistry: Laboratory studies of transition metal-containing free radicals and spectroscopic observations of molecular interstellar environments

NASA Astrophysics Data System (ADS)

Adande, Gilles Rapotchombo

Progress in our understanding of the chemical composition of the interstellar medium leans both on laboratory analyses of high resolution rotational spectra from molecules that may be present in these regions, and on radio astronomical observations of molecular tracers to constrain astrochemical models. Due to the thermodynamic conditions in outer space, some molecules likely to be found in interstellar regions in relevant abundances are open shell radicals. In a series of laboratory studies, the pure rotational spectra of the transition metal containing radicals sulfur species ScS, YS, VS and ZnSH were obtained for the first time. In addition to accurate and precise rest frequencies for these species, bonding characteristics were determined from fine and hyperfine molecular parameters. It was found that these sulfides have a higher degree of covalent bonding than their mostly ionic oxide counterparts. Isomers and isotope ratios are excellent diagnostic tools for a variety of astrochemical models. From radio observations of isotopes of nitrile species, the galactic gradient of 14N/15N was accurately established. A further study of this ratio in carbon rich asymptotic giant branch stars provided observational evidence for an unknown process in J type carbon stars, and highlighted the need to update stellar nucleosynthesis models. Proper radiative transfer modeling of the emission spectra of interstellar molecules can yield a wealth of information about the abundance and distribution of these species within the observed sources. To model the asymmetric emission of SO and SO2 in oxygen-rich supergiants, an in-house code was developed, and successfully applied to gain insight into circumstellar sulfur chemistry of VY Canis Majoris. It was concluded that current astrochemistry kinetic models, based on spherical symmetry assumptions, need to be revisited.

The solvation study of carbon, silicon and their mixed nanotubes in water solution.

PubMed

Hashemi Haeri, Haleh; Ketabi, Sepideh; Hashemianzadeh, Seyed Majid

2012-07-01

Nanotubes are believed to open the road toward different modern fields, either technological or biological. However, the applications of nanotubes have been badly impeded for the poor solubility in water which is especially essential for studies in the presence of living cells. Therefore, water soluble samples are in demand. Herein, the outcomes of Monte Carlo simulations of different sets of multiwall nanotubes immersed in water are reported. A number of multi wall nanotube samples, comprised of pure carbon, pure silicon and several mixtures of carbon and silicon are the subjects of study. The simulations are carried out in an (N,V,T) ensemble. The purpose of this report is to look at the effects of nanotube size (diameter) and nanotube type (pure carbon, pure silicon or a mixture of carbon and silicon) variation on solubility of multiwall nanotubes in terms of number of water molecules in shell volume. It is found that the solubility of the multi wall carbon nanotube samples is size independent, whereas multi wall silicon nanotube samples solubility varies with diameter of the inner tube. The higher solubility of samples containing silicon can be attributed to the larger atomic size of silicon atom which provides more direct contact with the water molecules. The other affecting factor is the bigger inter space (the space between inner and outer tube) in the case of silicon samples. Carbon type multi wall nanotubes appeared as better candidates for transporting water molecules through a multi wall nanotube structure, while in the case of water adsorption problems it is better to use multi wall silicon nanotubes or a mixture of multi wall carbon/ silicon nanotubes.

The Acinar Cage: Basement Membranes Determine Molecule Exchange and Mechanical Stability of Human Breast Cell Acini.

PubMed

Gaiko-Shcherbak, Aljona; Fabris, Gloria; Dreissen, Georg; Merkel, Rudolf; Hoffmann, Bernd; Noetzel, Erik

2015-01-01

The biophysical properties of the basement membrane that surrounds human breast glands are poorly understood, but are thought to be decisive for normal organ function and malignancy. Here, we characterize the breast gland basement membrane with a focus on molecule permeation and mechanical stability, both crucial for organ function. We used well-established and nature-mimicking MCF10A acini as 3D cell model for human breast glands, with ether low- or highly-developed basement membrane scaffolds. Semi-quantitative dextran tracer (3 to 40 kDa) experiments allowed us to investigate the basement membrane scaffold as a molecule diffusion barrier in human breast acini in vitro. We demonstrated that molecule permeation correlated positively with macromolecule size and intriguingly also with basement membrane development state, revealing a pore size of at least 9 nm. Notably, an intact collagen IV mesh proved to be essential for this permeation function. Furthermore, we performed ultra-sensitive atomic force microscopy to quantify the response of native breast acini and of decellularized basement membrane shells against mechanical indentation. We found a clear correlation between increasing acinar force resistance and basement membrane formation stage. Most important native acini with highly-developed basement membranes as well as cell-free basement membrane shells could both withstand physiologically relevant loads (≤ 20 nN) without loss of structural integrity. In contrast, low-developed basement membranes were significantly softer and more fragile. In conclusion, our study emphasizes the key role of the basement membrane as conductor of acinar molecule influx and mechanical stability of human breast glands, which are fundamental for normal organ function.

A generalized operational formula based on total electronic densities to obtain 3D pictures of the dual descriptor to reveal nucleophilic and electrophilic sites accurately on closed-shell molecules.

PubMed

Martínez-Araya, Jorge I

2016-09-30

By means of the conceptual density functional theory, the so-called dual descriptor (DD) has been adapted to be used in any closed-shell molecule that presents degeneracy in its frontier molecular orbitals. The latter is of paramount importance because a correct description of local reactivity will allow to predict the most favorable sites on a molecule to undergo nucleophilic or electrophilic attacks; on the contrary, an incomplete description of local reactivity might have serio us consequences, particularly for those experimental chemists that have the need of getting an insight about reactivity of chemical reagents before using them in synthesis to obtain a new compound. In the present work, the old approach based only on electronic densities of frontier molecular orbitals is replaced by the most accurate procedure that implies the use of total electronic densities thus keeping consistency with the essential principle of the DFT in which the electronic density is the fundamental variable and not the molecular orbitals. As a result of the present work, the DD will be able to properly describe local reactivities only in terms of total electronic densities. To test the proposed operational formula, 12 very common molecules were selected as the original definition of the DD was not able to describe their local reactivities properly. The ethylene molecule was additionally used to test the capability of the proposed operational formula to reveal a correct local reactivity even in absence of degeneracy in frontier molecular orbitals. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

GAUSSIAN 76: An ab initio Molecular Orbital Program

DOE R&D Accomplishments Database

Binkley, J. S.; Whiteside, R.; Hariharan, P. C.; Seeger, R.; Hehre, W. J.; Lathan, W. A.; Newton, M. D.; Ditchfield, R.; Pople, J. A.

1978-01-01

Gaussian 76 is a general-purpose computer program for ab initio Hartree-Fock molecular orbital calculations. It can handle basis sets involving s, p and d-type Gaussian functions. Certain standard sets (STO-3G, 4-31G, 6-31G*, etc.) are stored internally for easy use. Closed shell (RHF) or unrestricted open shell (UHF) wave functions can be obtained. Facilities are provided for geometry optimization to potential minima and for limited potential surface scans.

Biotin-decorated silica coated PbS nanocrystals emitting in the second biological near infrared window for bioimaging

NASA Astrophysics Data System (ADS)

Corricelli, M.; Depalo, N.; di Carlo, E.; Fanizza, E.; Laquintana, V.; Denora, N.; Agostiano, A.; Striccoli, M.; Curri, M. L.

2014-06-01

Nanoparticles (NPs) emitting in the second biological near infrared (NIR) window of the electromagnetic spectrum have been successfully synthesized by growing a silica shell on the hydrophobic surface of OLEA/TOP PbS nanocrystals (NCs), by means of a reverse microemulsion approach, and subsequently decorated with biotin molecules. The fabrication of very uniform and monodisperse NPs, formed of SiO2 shell coated single core PbS NCs, has been demonstrated by means of a set of complementary optical and structural techniques (Vis-NIR absorption and photoluminescence spectroscopy, transmission electron microscopy) that have highlighted how experimental parameters, such as PbS NC and silica precursor concentration, are crucial to direct the morphology and optical properties of silica coated PbS NPs. Subsequently, the silica surface of the core-shell NPs has been grafted with amino groups, in order to achieve covalent binding of biotin to NIR emitting silica coated NPs. Finally the successful reaction with a green-fluorescent labelled streptavidin has verified the molecular recognition response of the biotin molecules decorating the PbS@SiO2 NP surface. Dynamic light scattering (DLS) and ζ-potential techniques have been used to monitor the hydrodynamic diameter and colloidal stability of both PbS@SiO2 and biotin decorated NPs, showing their high colloidal stability in physiological media, as needed for biomedical applications. Remarkably the obtained biotinylated PbS@SiO2 NPs have been found to retain emission properties in the `second optical window' of the NIR region of the electromagnetic spectrum, thus representing attractive receptor-targeted NIR fluorescent probes for in vivo tumour imaging.Nanoparticles (NPs) emitting in the second biological near infrared (NIR) window of the electromagnetic spectrum have been successfully synthesized by growing a silica shell on the hydrophobic surface of OLEA/TOP PbS nanocrystals (NCs), by means of a reverse microemulsion approach, and subsequently decorated with biotin molecules. The fabrication of very uniform and monodisperse NPs, formed of SiO2 shell coated single core PbS NCs, has been demonstrated by means of a set of complementary optical and structural techniques (Vis-NIR absorption and photoluminescence spectroscopy, transmission electron microscopy) that have highlighted how experimental parameters, such as PbS NC and silica precursor concentration, are crucial to direct the morphology and optical properties of silica coated PbS NPs. Subsequently, the silica surface of the core-shell NPs has been grafted with amino groups, in order to achieve covalent binding of biotin to NIR emitting silica coated NPs. Finally the successful reaction with a green-fluorescent labelled streptavidin has verified the molecular recognition response of the biotin molecules decorating the PbS@SiO2 NP surface. Dynamic light scattering (DLS) and ζ-potential techniques have been used to monitor the hydrodynamic diameter and colloidal stability of both PbS@SiO2 and biotin decorated NPs, showing their high colloidal stability in physiological media, as needed for biomedical applications. Remarkably the obtained biotinylated PbS@SiO2 NPs have been found to retain emission properties in the `second optical window' of the NIR region of the electromagnetic spectrum, thus representing attractive receptor-targeted NIR fluorescent probes for in vivo tumour imaging. Electronic supplementary information (ESI) available: Size statistical analysis of silanized PbS NPs, TLC plate showing the ninhydrin test results and a table summarizing the DH and ζ-potential values for the investigated samples. See DOI: 10.1039/c4nr01025f

An efficient parallel algorithm for the calculation of unrestricted canonical MP2 energies.

PubMed

Baker, Jon; Wolinski, Krzysztof

2011-11-30

We present details of our efficient implementation of full accuracy unrestricted open-shell second-order canonical Møller-Plesset (MP2) energies, both serial and parallel. The algorithm is based on our previous restricted closed-shell MP2 code using the Saebo-Almlöf direct integral transformation. Depending on system details, UMP2 energies take from less than 1.5 to about 3.0 times as long as a closed-shell RMP2 energy on a similar system using the same algorithm. Several examples are given including timings for some large stable radicals with 90+ atoms and over 3600 basis functions. Copyright © 2011 Wiley Periodicals, Inc.

User document for computer programs for ring-stiffened shells of revolution

NASA Technical Reports Server (NTRS)

Cohen, G. A.

1973-01-01

A user manual and related program documentation is presented for six compatible computer programs for structural analysis of axisymmetric shell structures. The programs apply to a common structural model but analyze different modes of structural response. In particular, they are: (1) Linear static response under asymmetric loads; (2) Buckling of linear states under asymmetric loads; (3) Nonlinear static response under axisymmetric loads; (4) Buckling nonlinear states under axisymmetric (5) Imperfection sensitivity of buckling modes under axisymmetric loads; and (6) Vibrations about nonlinear states under axisymmetric loads. These programs treat branched shells of revolution with an arbitrary arrangement of a large number of open branches but with at most one closed branch.

Novel core-shell (TiO2@Silica) nanoparticles for scattering medium in a random laser: higher efficiency, lower laser threshold and lower photodegradation.

PubMed

Jimenez-Villar, Ernesto; Mestre, Valdeci; de Oliveira, Paulo C; de Sá, Gilberto F

2013-12-21

There has been growing interest in scattering media in recent years, due to their potential applications as solar collectors, photocatalyzers, random lasers and other novel optical devices. Here, we have introduced a novel core-shell scattering medium for a random laser composed of TiO2@Silica nanoparticles. Higher efficiency, lower laser threshold and long photobleaching lifetime in random lasers were demonstrated. This has introduced a new method or parameter (fraction of absorbed pumping), which opens a new avenue to characterize and study the scattering media. Optical chemical and colloidal stabilities were combined by coating a suitable silica shell onto TiO2 nanoparticles.

Liquid level controller

DOEpatents

Mangus, J.D.; Redding, A.H.

1975-07-15

A system for maintaining two distinct sodium levels within the shell of a heat exchanger having a plurality of J-shaped modular tube bundles each enclosed in a separate shell which extends from a common base portion. A lower liquid level is maintained in the base portion and an upper liquid level is maintained in the shell enwrapping the long stem of the J-shaped tube bundles by utilizing standpipes with a notch at the lower end which decreases in open area the distance from the end of the stand pipe increases and a supply of inert gas fed at a constant rate to produce liquid levels, which will remain generally constant as the flow of liquid through the vessel varies. (auth)

Shoulder replacement

MedlinePlus

... the opening at the end of the shoulder blade, called the socket. This type of joint allows ... head. The socket part (glenoid) of your shoulder blade will be replaced with a smooth plastic shell ( ...

Latitudinal distributions and composition of radiation on open drift shells in the altitude range 200 to 400 km

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

Tsaplin, V.S.; Shavrin, P.I.; Savun, O.I.

1973-01-01

S>Translated from Kosm. Issled.; 11: No. 4, 563-573(1973). An account of ihe results of measurements made on the satellites Kosmos 138, Kosmos 137, and Kosmos 219 in 1966-1967 is given. The latitudinal distributions of radiation in different energy ranges in the region with h/sub min/< 0 were obtained. A relationship between the intensity of the soft component and the geomagnetic activity was found. Information regarding the composition of the rsdiation on open drift shells in a wide range of latitudes is derived from a comparison of the data of various detectors. The paper concludes with a brief review of ihemore » results of measurement of local radiation on different vehicles. (auth)« less

Surface characterization of hydrophobic core-shell QDs using NMR techniques

NASA Astrophysics Data System (ADS)

Zhang, Chengqi; Zeng, Birong; Palui, Goutam; Mattoussi, Hedi

2018-02-01

Using a few solution phase NMR spectroscopy techniques, including 1H NMR and 31P NMR, we have characterized the organic shell on CdSe-ZnS core-shell quantum dots and tracked changes in its composition when the QD dispersions are subjected to varying degrees of purification. Combining solution phase NMR with diffusion ordered spectroscopy (DOSY), we were able to distinguish between freely diffusing ligands in the sample from those bound on the surfaces. Additionally, matrix assisted laser desorption ionization (MALDI) and FTIR measurements were used to provide complementary and supporting information on the organic ligand coating for these nanocrystals. We found that the organic shell is dominated by monomeric or oligomeric n-hexylphosphonic acid (HPA), along with small portion of 1-hexadecyl amine (HDA). The presence of TOP/TOPO (tri-n-octylphosphine / tri-noctylphosphine oxide) molecules is much smaller, even though large excess of TOP/TOPO were used during the QD growth. These results indicate that HPA (alkyl phosphonate) exhibits the strongest coordination affinity to ZnS-rich QD surfaces grown using the high temperature injection route.

Localized surface plasmon mediated energy transfer in the vicinity of core-shell nanoparticle

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

Shishodia, Manmohan Singh, E-mail: manmohan@gbu.ac.in; Juneja, Soniya

2016-05-28

Multipole spectral expansion based theory of energy transfer interactions between a donor and an acceptor molecule in the vicinity of a core-shell (nanoshell or core@shell) based plasmonic nanostructure is developed. In view of the diverse applications and rich plasmonic features such as tuning capability of surface plasmon (SP) frequencies, greater sensitivity to the change of dielectric environment, controllable redirection of electromagnetic radiation, closed form expressions for Energy Transfer Rate Enhancement Factor (ETREF) near core-shell particle are reported. The dependence of ETREF on different parameters is established through fitting equations, perceived to be of key importance for developing appropriate designs. Themore » theoretical approach developed in the present work is capable of treating higher order multipoles, which, in turn, are also shown to play a crucial role in the present context. Moreover, closed form expressions derived in the present work can directly be used as formula, e.g., for designing SP based biosensors and estimating energy exchange between proteins and excitonic interactions in quantum dots.« less

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

Demin, V. A., E-mail: victordemin88@gmail.com; Blank, V. D.; Karaeva, A. R.

A new fully carbon nanocomposite material is synthesized by the immersion of carbon nanotubes in a fullerene solution in carbon disulfide. The presence of a dense layer of fullerene molecules on the outer nanotube surface is demonstrated by TEM and XPS. Fullerenes are redistributed on the nanotube surface during a long-term action of an electron beam, which points to the existence of a molecular bond between a nanotube and fullerenes. Theoretical calculations show that the formation of a fullerene shell begins with the attachment of one C{sub 60} molecule to a defect on the nanotube surface.

Covalent Binding with Neutrons on the Femto-scale

NASA Astrophysics Data System (ADS)

von Oertzen, W.; Kanada-En'yo, Y.; Kimura, M.

2017-06-01

In light nuclei we have well defined clusters, nuclei with closed shells, which serve as centers for binary molecules with covalent binding by valence neutrons. Single neutron orbitals in light neutron-excess nuclei have well defined shell model quantum numbers. With the combination of two clusters and their neutron valence states, molecular two-center orbitals are defined; in the two-center shell model we can place valence neutrons in a large variety of molecular two-center states, and the formation of Dimers becomes possible. The corresponding rotational bands point with their large moments of inertia and the Coriolis decoupling effect (for K = 1/2 bands) to the internal molecular orbital structure in these states. On the basis of these the neutron rich isotopes allow the formation of a large variety molecular structures on the nuclear scale. An extended Ikeda diagram can be drawn for these cases. Molecular bands in Be and Ne-isotopes are discussed as text-book examples.

Correlation of molecular valence- and K-shell photoionization resonances with bond lengths

NASA Technical Reports Server (NTRS)

Sheehy, J. A.; Gil, T. J.; Winstead, C. L.; Farren, R. E.; Langhoff, P. W.

1989-01-01

The relationship between the interatomic distance and the positions of valence-shell and K-shell sigma(asterisk) photoionization resonances is investigated theoretically for the molecules C2, F2, N2, O2, CO, NO, C2H2, C2H4, C2H6, HCN, H2CO, N20, CO2, and C2N2. The results of molecular-orbital computations are presented in three-dimensional diagrams, which are shown to be similar to the wave functions of a particle in a cylindrical well, confirming the validity of free-electron molecular-orbital (FEMO) approximations for modeling the potential along the symmetry axis. FEMO orbital energies and resonance positions are found to be in good agreement with previous theoretical and experimental results. Also included is a Feshbach-Fano analysis of the relevance of virtual-valence orbitals to the appearance of single-channel resonances in molecular photoionization cross sections.

Shell architecture: a novel proxy for paleotemperature reconstructions?

NASA Astrophysics Data System (ADS)

Milano, Stefania; Nehrke, Gernot; Wanamaker, Alan D., Jr.; Witbaard, Rob; Schöne, Bernd R.

2017-04-01

Mollusk shells are unique high-resolution paleoenvironmental archives. Their geochemical properties, such as oxygen isotope composition (δ18Oshell) and element-to-calcium ratios, are routinely used to estimate past environmental conditions. However, the existing proxies have certain drawbacks that can affect paleoreconstruction robustness. For instance, the estimation of water temperature of brackish and near-shore environments can be biased by the interdependency of δ18Oshell from multiple environmental variables (water temperature and δ18Owater). Likely, the environmental signature can be masked by physiological processes responsible for the incorporation of trace elements into the shell. The present study evaluated the use of shell structural properties as alternative environmental proxies. The sensitivity of shell architecture at µm and nm-scale to the environment was tested. In particular, the relationship between water temperature and microstructure formation was investigated. To enable the detection of potential structural changes, the shells of the marine bivalves Cerastoderma edule and Arctica islandica were analyzed with Scanning Electron Microscopy (SEM), nanoindentation and Confocal Raman Microscopy (CRM). These techniques allow a quantitative approach to the microstructural analysis. Our results show that water temperature induces a clear response in shell microstructure. A significant alteration in the morphometric characteristics and crystallographic orientation of the structural units was observed. Our pilot study suggests that shell architecture records environmental information and it has potential to be used as novel temperature proxy in near-shore and open ocean habitats.

Nano-Biotechnology in Using Enzymes for Environmental Remediation: Single-Enzyme Nanoparticles

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

Kim, Jungbae; Grate, Jay W.

2005-01-01

We have developed armored single-enzyme nanoparticles (SENs), which dramatically stabilize a protease (a-chymotrypsin, CT) by surrounding each enzyme molecule with a porous composite organic/inorganic shell of less than a few nanometers thick. The armored enzymes show no decrease in CT activity at 30°C for a day while free CT activity is rapidly reduced by orders of magnitude. The armored shell around CT is sufficiently thin and porous that it does not place any serious mass-transfer limitation of substrate. This unique approach will have a great impact in using enzymes in various fields, including environmental remediation.

Tunneling current spectroscopy of a nanostructure junction involving multiple energy levels.

PubMed

Kuo, David M-T; Chang, Yia-Chung

2007-08-24

A multilevel Anderson model is employed to simulate the system of a nanostructure tunnel junction with any number of one-particle energy levels. The tunneling current, including both shell-tunneling and shell-filling cases, is theoretically investigated via the nonequilibrium Green's function method. We obtain a closed form for the spectral function, which is used to analyze the complicated tunneling current spectra of a quantum dot or molecule embedded in a double-barrier junction. We also show that negative differential conductance can be observed in a quantum dot tunnel junction when the Coulomb interactions with neighboring quantum dots are taken into account.

Hypercubane: DFT-based prediction of an Oh-symmetric double-shell hydrocarbon

NASA Astrophysics Data System (ADS)

Pichierri, Fabio

2014-09-01

Using density functional theory we design a molecular analog of the four-dimensional hypercube or tesseract which we called hypercubane. The title hydrocarbon (C40H24) is Oh-symmetric like cubane and is characterized by a double-shell architecture. The perfluorinated analog of hypercubane also is stable with a positive value of the electron affinity. Removal of the C8 core from hypercubane yields a hollowed Oh-symmetric hydrocarbon with enough room to host a single atom/ion guest. The resonances of the NMR-active 13C and 1H nuclei have been computed so as to assist the spectroscopic identification of the predicted molecules.

On the microscopic fluctuations driving the NMR relaxation of quadrupolar ions in water

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

Carof, Antoine; Salanne, Mathieu; Rotenberg, Benjamin, E-mail: benjamin.rotenberg@upmc.fr

Nuclear Magnetic Resonance (NMR) relaxation is sensitive to the local structure and dynamics around the probed nuclei. The Electric Field Gradient (EFG) is the key microscopic quantity to understand the NMR relaxation of quadrupolar ions, such as {sup 7}Li{sup +}, {sup 23}Na{sup +}, {sup 25}Mg{sup 2+}, {sup 35}Cl{sup −}, {sup 39}K{sup +}, or {sup 133}Cs{sup +}. Using molecular dynamics simulations, we investigate the statistical and dynamical properties of the EFG experienced by alkaline, alkaline Earth, and chloride ions at infinite dilution in water. Specifically, we analyze the effect of the ionic charge and size on the distribution of the EFGmore » tensor and on the multi-step decay of its auto-correlation function. The main contribution to the NMR relaxation time arises from the slowest mode, with a characteristic time on the picosecond time scale. The first solvation shell of the ion plays a dominant role in the fluctuations of the EFG, all the more that the ion radius is small and its charge is large. We propose an analysis based on a simplified charge distribution around the ion, which demonstrates that the auto-correlation of the EFG, hence the NMR relaxation time, reflects primarily the collective translational motion of water molecules in the first solvation shell of the cations. Our findings provide a microscopic route to the quantitative interpretation of NMR relaxation measurements and open the way to the design of improved analytical theories for NMR relaxation for small ionic solutes, which should focus on water density fluctuations around the ion.« less

Stable Tearing and Buckling Responses of Unstiffened Aluminum Shells with Long Cracks

NASA Technical Reports Server (NTRS)

Starnes, James H., Jr.; Rose, Cheryl A.

1999-01-01

The results of an analytical and experimental study of the nonlinear response of thin, unstiffened, aluminum cylindrical shells with a long longitudinal crack are presented. The shells are analyzed with a nonlinear shell analysis code that accurately accounts for global and local structural response phenomena. Results are presented for internal pressure and for axial compression loads. The effect of initial crack length on the initiation of stable crack growth and unstable crack growth in typical shells subjected to internal pressure loads is predicted using geometrically nonlinear elastic-plastic finite element analyses and the crack-tip-opening angle (CTOA) fracture criterion. The results of these analyses and of the experiments indicate that the pressure required to initiate stable crack growth and unstable crack growth in a shell subjected to internal pressure loads decreases as the initial crack length increases. The effects of crack length on the prebuckling, buckling and postbuckling responses of typical shells subjected to axial compression loads are also described. For this loading condition, the crack length was not allowed to increase as the load was increased. The results of the analyses and of the experiments indicate that the initial buckling load and collapse load for a shell subjected to axial compression loads decrease as the initial crack length increases. Initial buckling causes general instability or collapse of a shell for shorter initial crack lengths. Initial buckling is a stable local response mode for longer initial crack lengths. This stable local buckling response is followed by a stable postbuckling response, which is followed by general or overall instability of the shell.

Stable Tearing and Buckling Responses of Unstiffened Aluminum Shells with Long Cracks

NASA Technical Reports Server (NTRS)

Starnes, James H., Jr.; Rose, Cheryl A.

1998-01-01

The results of an analytical and experimental study of the nonlinear response of thin, unstiffened, aluminum cylindrical shells with a long longitudinal crack are presented. The shells are analyzed with a nonlinear shell analysis code that accurately accounts for global and local structural response phenomena. Results are presented for internal pressure and for axial compression loads. The effect of initial crack length on the initiation of stable crack growth and unstable crack growth in typical shells subjected to internal pressure loads is predicted using geometrically nonlinear elastic-plastic finite element analyses and the crack-tip-opening angle (CTOA) fracture criterion. The results of these analyses and of the experiments indicate that the pressure required to initiate stable crack growth and unstable crack growth in a shell subjected to internal pressure loads decreases as the initial crack length increases. The effects of crack length on the prebuckling, buckling and postbuckling responses of typical shells subjected to axial compression loads are also described. For this loading condition, the crack length was not allowed to increase as the load was increased. The results of the analyses and of the experiments indicate that the initial buckling load and collapse load for a shell subjected to axial compression loads decrease as the initial crack length increases. Initial buckling causes general instability or collapse of a shell for shorter initial crack lengths. Initial buckling is a stable local response mode for longer initial crack lengths. This stable local buckling response is followed by a stable postbuckling response, which is followed by general or overall instability of the shell.

Inner and Outer Coordination Shells of Mg(2+) in CorA Selectivity Filter from Molecular Dynamics Simulations.

PubMed

Kitjaruwankul, Sunan; Wapeesittipan, Pattama; Boonamnaj, Panisak; Sompornpisut, Pornthep

2016-01-28

Structural data of CorA Mg(2+) channels show that the five Gly-Met-Asn (GMN) motifs at the periplasmic loop of the pentamer structure form a molecular scaffold serving as a selectivity filter. Unfortunately, knowledge about the cation selectivity of Mg(2+) channels remains limited. Since Mg(2+) in aqueous solution has a strong first hydration shell and apparent second hydration sphere, the coordination structure of Mg(2+) in a CorA selectivity filter is expected to be different from that in bulk water. Hence, this study investigated the hydration structure and ligand coordination of Mg(2+) in a selectivity filter of CorA using molecular dynamics (MD) simulations. The simulations reveal that the inner-shell structure of Mg(2+) in the filter is not significantly different from that in aqueous solution. The major difference is the characteristic structural features of the outer shell. The GMN residues engage indirectly in the interactions with the metal ion as ligands in the second shell of Mg(2+). Loss of hydrogen bonds between inner- and outer-shell waters observed from Mg(2+) in bulk water is mostly compensated by interactions between waters in the first solvation shell and the GMN motif. Some water molecules in the second shell remain in the selectivity filter and become less mobile to support the metal binding. Removal of Mg(2+) from the divalent cation sensor sites of the protein had an impact on the structure and metal binding of the filter. From the results, it can be concluded that the GMN motif enhances the affinity of the metal binding site in the CorA selectivity filter by acting as an outer coordination ligand.

Free Vibration Characteristics of Functionally Graded Pre-twisted Conical Shells under Rotation

NASA Astrophysics Data System (ADS)

Das, Apurba; Karmakar, Amit

2017-06-01

This article deals with effect of rotation and pretwist angle on free vibration characteristics of functionally graded conical shells. The dynamic equilibrium equation is derived from Lagrange's equation neglecting the Coriolis effect for moderate rotational speeds. The materials properties of conical shell are varied with a power-law distribution of the volume fractions of their constituents through its thickness. Convergence studies are performed in respect of mesh sizes, and comparisons of the present solutions and those reported in open literature are provided to substantiate the accuracy of the proposed method. Computer codes developed to obtain the numerical results for the combined effects of twist angle and rotational speed on the natural frequencies of functionally graded conical shells. The mode shapes for a typical laminate configuration under different conditions are also illustrated. Numerical results are obtained for the non-dimensional fundamental (NDFF) and second frequencies (NDSF).

Synthesis of Various Metal/TiO2 Core/shell Nanorod Arrays

NASA Astrophysics Data System (ADS)

Zhu, Wei; Wang, Guan-zhong; Hong, Xun; Shen, Xiao-shuang

2011-02-01

We present a general approach to fabricate metal/TiO2 core/shell nanorod structures by two-step electrodeposition. Firstly, TiO2 nanotubes with uniform wall thickness are prepared in anodic aluminum oxide (AAO) membranes by electrodeposition. The wall thickness of the nanotubes could be easily controlled by modulating the deposition time, and their outer diameter and length are only limited by the channel diameter and the thickness of the AAO membranes, respectively. The nanotubes' tops prepared by this method are open, while the bottoms are connected directly with the Au film at the back of the AAO membranes. Secondly, Pd, Cu, and Fe elements are filled into the TiO2 nanotubes to form core/shell structures. The core/shell nanorods prepared by this two-step process are high density and free-standing, and their length is dependent on the deposition time.

The stresses in stiffener openings

NASA Technical Reports Server (NTRS)

Marguerre, K

1942-01-01

The present study treats as a typical example a ring the center line of which is produced by the intersection of two circular cylinders of different diameter. Three load cases are analyzed: (1) Axial and circumferential stresses in both cylinders, the cylinder stresses themselves to be in the ratio conformal to the cylinders loaded under internal pressure. (2) Pure longitudinal tension in the large cylinder. (3) Pure shear (torsion) in the large cylinder. To simplify the calculation, it is assumed that the ring, compared to the shell, is very strong, so that its deformations have no perceptible effect on the stress condition in the shell. This provides an upper limit for the ring stresses actually produced in a shell design, for, according to the theory of stressed skin statics the shells, by elastic flexibility of the ring, regroup the forces deposited on it in such a manner that the ring is relieved.

Ab initio results for intermediate-mass, open-shell nuclei

NASA Astrophysics Data System (ADS)

Baker, Robert B.; Dytrych, Tomas; Launey, Kristina D.; Draayer, Jerry P.

2017-01-01

A theoretical understanding of nuclei in the intermediate-mass region is vital to astrophysical models, especially for nucleosynthesis. Here, we employ the ab initio symmetry-adapted no-core shell model (SA-NCSM) in an effort to push first-principle calculations across the sd-shell region. The ab initio SA-NCSM's advantages come from its ability to control the growth of model spaces by including only physically relevant subspaces, which allows us to explore ultra-large model spaces beyond the reach of other methods. We report on calculations for 19Ne and 20Ne up through 13 harmonic oscillator shells using realistic interactions and discuss the underlying structure as well as implications for various astrophysical reactions. This work was supported by the U.S. NSF (OCI-0904874 and ACI -1516338) and the U.S. DOE (DE-SC0005248), and also benefitted from the Blue Waters sustained-petascale computing project and high performance computing resources provided by LSU.

Helmet of a laminate construction of polycarbonate and polysulfone polymeric material

NASA Technical Reports Server (NTRS)

Kosmo, Joseph J. (Inventor); Dawn, Frederic S. (Inventor)

1991-01-01

An article of laminate construction is disclosed which is comprised of an underlayer of polycarbonate polymer material to which is applied a chemically resistant outer layer of polysulfone. The layers which are joined by compression-heat molding, are molded to form the shape of a body protective shell such as a space helmet comprising a shell of polycarbonate, polysulfone laminate construction attached at its open end to a sealing ring adapted for connection to a space suit. The front portion of the shell provides a transparent visor for the helmet. An outer visor of polycarbonate polysulfone laminate construction is pivotally mounted to the sealing ring for covering the transparent visor portion of the shell during extravehicular activities. The polycarbonate under layer of the outer visor is coated on its inner surface with a vacuum deposit of gold to provide additional thermal radiation resistance.

Vibration and bending behavior of functionally graded nanocomposite doubly-curved shallow shells reinforced by graphene nanoplatelets

NASA Astrophysics Data System (ADS)

Wang, Aiwen; Chen, Hongyan; Hao, Yuxin; Zhang, Wei

2018-06-01

Free vibration and static bending of functionally graded (FG) graphene nanoplatelet (GPL) reinforced composite doubly-curved shallow shells with three distinguished distributions are analyzed. Material properties with gradient variation in the thickness aspect are evaluated by the modified Halpin-Tsai model. Mathematical model of the simply supported doubly-curved shallow shells rests upon Hamilton Principle and a higher order shear deformation theory (HSDT). The free vibration frequencies and bending deflections are gained by taking into account Navier technique. The agreement between the obtained results and ANSYS as well as the prior results in the open literature verifies the accuracy of the theory in this article. Further, parametric studies are accomplished to highlight the significant influence of GPL distribution patterns and weight fraction, stratification number, dimensions of GPLs and shells on the mechanical behavior of the system.

Nonpolar InGaN/GaN Core-Shell Single Nanowire Lasers.

PubMed

Li, Changyi; Wright, Jeremy B; Liu, Sheng; Lu, Ping; Figiel, Jeffrey J; Leung, Benjamin; Chow, Weng W; Brener, Igal; Koleske, Daniel D; Luk, Ting-Shan; Feezell, Daniel F; Brueck, S R J; Wang, George T

2017-02-08

We report lasing from nonpolar p-i-n InGaN/GaN multi-quantum well core-shell single-nanowire lasers by optical pumping at room temperature. The nanowire lasers were fabricated using a hybrid approach consisting of a top-down two-step etch process followed by a bottom-up regrowth process, enabling precise geometrical control and high material gain and optical confinement. The modal gain spectra and the gain curves of the core-shell nanowire lasers were measured using micro-photoluminescence and analyzed using the Hakki-Paoli method. Significantly lower lasing thresholds due to high optical gain were measured compared to previously reported semipolar InGaN/GaN core-shell nanowires, despite significantly shorter cavity lengths and reduced active region volume. Mode simulations show that due to the core-shell architecture, annular-shaped modes have higher optical confinement than solid transverse modes. The results show the viability of this p-i-n nonpolar core-shell nanowire architecture, previously investigated for next-generation light-emitting diodes, as low-threshold, coherent UV-visible nanoscale light emitters, and open a route toward monolithic, integrable, electrically injected single-nanowire lasers operating at room temperature.

Nonpolar InGaN/GaN core–shell single nanowire lasers

DOE PAGES

Li, Changyi; Wright, Jeremy Benjamin; Liu, Sheng; ...

2017-01-24

We report lasing from nonpolar p-i-n InGaN/GaN multi-quantum well core–shell single-nanowire lasers by optical pumping at room temperature. The nanowire lasers were fabricated using a hybrid approach consisting of a top-down two-step etch process followed by a bottom-up regrowth process, enabling precise geometrical control and high material gain and optical confinement. The modal gain spectra and the gain curves of the core–shell nanowire lasers were measured using micro-photoluminescence and analyzed using the Hakki-Paoli method. Significantly lower lasing thresholds due to high optical gain were measured compared to previously reported semipolar InGaN/GaN core–shell nanowires, despite significantly shorter cavity lengths and reducedmore » active region volume. Mode simulations show that due to the core–shell architecture, annular-shaped modes have higher optical confinement than solid transverse modes. Furthermore, the results show the viability of this p-i-n nonpolar core–shell nanowire architecture, previously investigated for next-generation light-emitting diodes, as low-threshold, coherent UV–visible nanoscale light emitters, and open a route toward monolithic, integrable, electrically injected single-nanowire lasers operating at room temperature.« less

Bessel Fourier orientation reconstruction: an analytical EAP reconstruction using multiple shell acquisitions in diffusion MRI.

PubMed

Hosseinbor, Ameer Pasha; Chung, Moo K; Wu, Yu-Chien; Alexander, Andrew L

2011-01-01

The estimation of the ensemble average propagator (EAP) directly from q-space DWI signals is an open problem in diffusion MRI. Diffusion spectrum imaging (DSI) is one common technique to compute the EAP directly from the diffusion signal, but it is burdened by the large sampling required. Recently, several analytical EAP reconstruction schemes for multiple q-shell acquisitions have been proposed. One, in particular, is Diffusion Propagator Imaging (DPI) which is based on the Laplace's equation estimation of diffusion signal for each shell acquisition. Viewed intuitively in terms of the heat equation, the DPI solution is obtained when the heat distribution between temperatuere measurements at each shell is at steady state. We propose a generalized extension of DPI, Bessel Fourier Orientation Reconstruction (BFOR), whose solution is based on heat equation estimation of the diffusion signal for each shell acquisition. That is, the heat distribution between shell measurements is no longer at steady state. In addition to being analytical, the BFOR solution also includes an intrinsic exponential smootheing term. We illustrate the effectiveness of the proposed method by showing results on both synthetic and real MR datasets.

The argonaut shell: gas-mediated buoyancy control in a pelagic octopus.

PubMed

Finn, Julian K; Norman, Mark D

2010-10-07

Argonauts (Cephalopoda: Argonautidae) are a group of rarely encountered open-ocean pelagic octopuses with benthic ancestry. Female argonauts inhabit a brittle 'paper nautilus' shell, the role of which has puzzled naturalists for millennia. The primary role attributed to the shell has been as a receptacle for egg deposition and brooding. Our observations of wild argonauts have revealed that the thin calcareous shell also functions as a hydrostatic structure, employed by the female argonaut to precisely control buoyancy at varying depths. Female argonauts use the shell to 'gulp' a measured volume of air at the sea surface, seal off the captured gas using flanged arms and forcefully dive to a depth where the compressed gas buoyancy counteracts body weight. This process allows the female argonaut to attain neutral buoyancy at depth and potentially adjust buoyancy to counter the increased (and significant) weight of eggs during reproductive periods. Evolution of this air-capture strategy enables this negatively buoyant octopus to survive free of the sea floor. This major shift in life mode from benthic to pelagic shows strong evolutionary parallels with the origins of all cephalopods, which attained gas-mediated buoyancy via the closed-chambered shells of the true nautiluses and their relatives.

An unusual occurrence of Nautilus macromphalus in a cenote in the Loyalty Islands (New Caledonia).

PubMed

Landman, Neil H; Mapes, Royal H; Cochran, J Kirk; Lignier, Vincent; Hembree, Daniel I; Goiran, Claire; Folcher, Eric; Brunet, Philippe

2014-01-01

Exploration of a landlocked cenote on Lifou (Loyalty Islands) revealed 37 shells of the cephalopod Nautilus macromphalus Sowerby, 1849, in saltwater on the cenote floor, approximately 40 m below the water surface. The occurrence of these shells is unusual because N. macromphalus is restricted to the open marine waters surrounding the island. All of the shells are mature, and nearly all of them are unbroken, with faded red-brown color stripes. We analyzed seven shells to determine their age. Radiocarbon dating yielded ages of 6380±30 to 7095±30 y BP. The 238U-series radionuclides 210Pb (half-life  = 22.3 y) and 226Ra (half-life  = 1600 y) also were measured. Two of the samples showed radioactive equilibrium between the nuclides, consistent with the old radiocarbon dates, but the other five samples showed excess 210Pb. When corrected for radioactive decay, the 226Ra activities were much greater than those found in living Nautilus. We conclude that exposure to high activities of 222Rn and 226Ra in the salty groundwater of the cenote altered the activities originally incorporated into the shells. Human placement of the shells in the cavity is rejected based on their radiocarbon age and the geometry of the cenote. The most probable explanation is that the animals entered the flooded karstic system through a connection on the seaward side at approximately 7,000 y BP, during an interval of slowly rising sea level. Unable to find an exit and/or due to anoxic bottom waters, the animals were trapped and died inside. The open connection with the sea persisted for ∼700 y, but after ∼6400 y BP, the connection was lost, probably due to a roof collapse. This is a rare example of Nautilus in a karstic coastal basin and provides a minimum age for the appearance of N. macromphalus in the Loyalty Islands.

An Unusual Occurrence of Nautilus macromphalus in a Cenote in the Loyalty Islands (New Caledonia)

PubMed Central

Landman, Neil H.; Mapes, Royal H.; Cochran, J. Kirk; Lignier, Vincent; Hembree, Daniel I.; Goiran, Claire; Folcher, Eric; Brunet, Philippe

2014-01-01

Exploration of a landlocked cenote on Lifou (Loyalty Islands) revealed 37 shells of the cephalopod Nautilus macromphalus Sowerby, 1849, in saltwater on the cenote floor, approximately 40 m below the water surface. The occurrence of these shells is unusual because N. macromphalus is restricted to the open marine waters surrounding the island. All of the shells are mature, and nearly all of them are unbroken, with faded red-brown color stripes. We analyzed seven shells to determine their age. Radiocarbon dating yielded ages of 6380±30 to 7095±30 y BP. The 238U-series radionuclides 210Pb (half-life  = 22.3 y) and 226Ra (half-life  = 1600 y) also were measured. Two of the samples showed radioactive equilibrium between the nuclides, consistent with the old radiocarbon dates, but the other five samples showed excess 210Pb. When corrected for radioactive decay, the 226Ra activities were much greater than those found in living Nautilus. We conclude that exposure to high activities of 222Rn and 226Ra in the salty groundwater of the cenote altered the activities originally incorporated into the shells. Human placement of the shells in the cavity is rejected based on their radiocarbon age and the geometry of the cenote. The most probable explanation is that the animals entered the flooded karstic system through a connection on the seaward side at approximately 7,000 y BP, during an interval of slowly rising sea level. Unable to find an exit and/or due to anoxic bottom waters, the animals were trapped and died inside. The open connection with the sea persisted for ∼700 y, but after ∼6400 y BP, the connection was lost, probably due to a roof collapse. This is a rare example of Nautilus in a karstic coastal basin and provides a minimum age for the appearance of N. macromphalus in the Loyalty Islands. PMID:25470257

Spin-adapted open-shell random phase approximation and time-dependent density functional theory. I. Theory.

PubMed

Li, Zhendong; Liu, Wenjian

2010-08-14

The spin-adaptation of single-reference quantum chemical methods for excited states of open-shell systems has been nontrivial. The primary reason is that the configuration space, generated by a truncated rank of excitations from only one component of a reference multiplet, is spin-incomplete. Those "missing" configurations are of higher ranks and can, in principle, be recaptured by a particular class of excitation operators. However, the resulting formalisms are then quite involved and there are situations [e.g., time-dependent density functional theory (TD-DFT) under the adiabatic approximation] that prevent one from doing so. To solve this issue, we propose here a tensor-coupling scheme that invokes all the components of a reference multiplet (i.e., a tensor reference) rather than increases the excitation ranks. A minimal spin-adapted n-tuply excited configuration space can readily be constructed by tensor products between the n-tuple tensor excitation operators and the chosen tensor reference. Further combined with the tensor equation-of-motion formalism, very compact expressions for excitation energies can be obtained. As a first application of this general idea, a spin-adapted open-shell random phase approximation is first developed. The so-called "translation rule" is then adopted to formulate a spin-adapted, restricted open-shell Kohn-Sham (ROKS)-based TD-DFT (ROKS-TD-DFT). Here, a particular symmetry structure has to be imposed on the exchange-correlation kernel. While the standard ROKS-TD-DFT can access only excited states due to singlet-coupled single excitations, i.e., only some of the singly excited states of the same spin (S(i)) as the reference, the new scheme can capture all the excited states of spin S(i)-1, S(i), or S(i)+1 due to both singlet- and triplet-coupled single excitations. The actual implementation and computation are very much like the (spin-contaminated) unrestricted Kohn-Sham-based TD-DFT. It is also shown that spin-contaminated spin-flip configuration interaction approaches can easily be spin-adapted via the tensor-coupling scheme.

Heat exchanger

DOEpatents

Brackenbury, Phillip J.

1986-01-01

A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

Heat exchanger

DOEpatents

Brackenbury, P.J.

1983-12-08

A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

Ultrasonic Device Would Open Pipe Bombs

NASA Technical Reports Server (NTRS)

El-Raheb, Michael S.; Adams, Marc A.; Zwissler, James G.

1991-01-01

Piezoelectric ultrasonic transducer, energized by frequency generator and power supply, vibrates shell of pipe bomb while hardly disturbing explosive inner material. Frequency-control circuitry senses resonance in shell and holds generator at that frequency to induce fatigue cracking in threads of end cap. In addition to disarming bombs, ultrasonically induced fatigue may have other applications. In manufacturing, replaces some machining and cutting operations. In repair of equipment, cleanly and quickly disassembles corroded parts. In demolition of buildings used to dismember steel framework safely and controllably.

Heat exchanger

DOEpatents

Brackenbury, Phillip J.

1986-04-01

A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

6. VIEW TO THE NORTHEAST OF WEST BOILER ROOM LUDOWICI ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

6. VIEW TO THE NORTHEAST OF WEST BOILER ROOM LUDOWICI TILE ROOF. THE ROOF OVER THE TURBINE HALL IN THE RIGHT FOREGROUND WAS REPLACED JUST PRIOR TO THE PLANT'S SHUTDOWN IN 1986. SEAGULLS DROP SHELLFISH ON THE HARD LUDOWICI TILE ROOF TO BREAK THEM OPEN. THE WHITE PARTICLES ON THE TILE ROOF ARE SHELL FRAGMENTS. NOTE THE RELATIVE LACK OF SHELLS ON THE SOFTER ASPHALT COMPOSITION ROOF. - New York, New Haven & Hartford Railroad, Cos Cob Power Plant, Sound Shore Drive, Greenwich, Fairfield County, CT

Study of open systems with molecules in isotropic liquids

NASA Astrophysics Data System (ADS)

Kondo, Yasushi; Matsuzaki, Masayuki

2018-05-01

We are interested in dynamics of a system in an environment, or an open system. Such phenomena as crossover from Markovian to non-Markovian relaxation and thermal equilibration are of our interest. Open systems have experimentally been studied with ultra cold atoms, ions in traps, optics, and cold electric circuits because well-isolated systems can be prepared here and thus the effects of environments can be controlled. We point out that some molecules solved in isotropic liquid are well isolated and thus they can also be employed for studying open systems in Nuclear Magnetic Resonance (NMR) experiments. First, we provide a short review on related phenomena of open systems that helps readers to understand our motivation. We, then, present two experiments as examples of our approach with molecules in isotropic liquids. Crossover from Markovian to non-Markovian relaxation was realized in one NMR experiment, while relaxation-like phenomena were observed in approximately isolated systems in the other.

Photodissociation spectroscopy of the dysprosium monochloride molecular ion

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

Dunning, Alexander, E-mail: alexander.dunning@gmail.com; Schowalter, Steven J.; Puri, Prateek

2015-09-28

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells,more » including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.« less

The heat of formation of gaseous PuO(2)2+ from relativistic density functional calculations.

PubMed

Moskaleva, Lyudmila V; Matveev, Alexei V; Dengler, Joachim; Rösch, Notker

2006-08-28

Using a set of model reactions, we estimated the heat of formation of gaseous PuO2(2+) from quantum-chemical reaction enthalpies and experimental heats of formation of reference species. To this end, we carried out relativistic density functional calculations on the molecules PuO(2)2+, PuO2, PuF6, and PuF4. We used a revised variant (PBEN) of the Perdew-Burke-Ernzerhof gradient-corrected exchange-correlation functional, and we accounted for spin-orbit interaction in a self-consistent fashion. As open-shell Pu species with two or more unpaired 5f electrons are involved, spin-orbit interaction significantly affects the energies of the model reactions. Our theoretical estimate for the heat of formation DeltafH degree 0(PuO2(2+),g), 418+/-15 kcal mol-1, evaluated using plutonium fluorides as references, is in good agreement with a recent experimental result, 413+/-16 kcal mol-1. The theoretical value connected to the experimental heat of formation of PuO2(g) has a notably higher uncertainty and therefore was not included in the final result.

Gas turbine engine adapted for use in combination with an apparatus for separating a portion of oxygen from compressed air

DOEpatents

Bland, Robert J [Oviedo, FL; Horazak, Dennis A [Orlando, FL

2012-03-06

A gas turbine engine is provided comprising an outer shell, a compressor assembly, at least one combustor assembly, a turbine assembly and duct structure. The outer shell includes a compressor section, a combustor section, an intermediate section and a turbine section. The intermediate section includes at least one first opening and at least one second opening. The compressor assembly is located in the compressor section to define with the compressor section a compressor apparatus to compress air. The at least one combustor assembly is coupled to the combustor section to define with the combustor section a combustor apparatus. The turbine assembly is located in the turbine section to define with the turbine section a turbine apparatus. The duct structure is coupled to the intermediate section to receive at least a portion of the compressed air from the compressor apparatus through the at least one first opening in the intermediate section, pass the compressed air to an apparatus for separating a portion of oxygen from the compressed air to produced vitiated compressed air and return the vitiated compressed air to the intermediate section via the at least one second opening in the intermediate section.

Nineteenth-century collapse of a benthic marine ecosystem on the open continental shelf

PubMed Central

Tomašových, Adam; Kidwell, Susan M.

2017-01-01

The soft-sediment seafloor of the open continental shelf is among the least-known biomes on Earth, despite its high diversity and importance to fisheries and biogeochemical cycling. Abundant dead shells of epifaunal suspension-feeding terebratulid brachiopods (Laqueus) and scallops on the now-muddy mainland continental shelf of southern California reveal the recent, previously unsuspected extirpation of an extensive offshore shell-gravel ecosystem, evidently driven by anthropogenic siltation. Living populations of attached epifauna, which formerly existed in a middle- and outer-shelf mosaic with patches of trophically diverse muds, are restricted today to rocky seafloor along the shelf edge and to the sandier shelves of offshore islands. Geological age-dating of 190 dead brachiopod shells shows that (i) no shells have been produced on the mainland shelf within the last 100 years, (ii) their shell production declined steeply during the nineteenth century, and (iii) they had formerly been present continuously for at least 4 kyr. This loss, sufficiently rapid (less than or equal to 100 years) and thorough to represent an ecosystem collapse, coincides with intensification of alluvial-plain land use in the nineteenth century, particularly livestock grazing. Extirpation was complete by the start of twentieth-century urbanization, warming, bottom fishing and scientific surveys. The loss of this filter-feeding fauna and the new spatial homogeneity and dominance of deposit- and detritus-feeders would have altered ecosystem functioning by reducing habitat heterogeneity and seawater filtering. This discovery, attesting to the power of this geological approach to recent ecological transitions, also strongly increases the spatial scope attributable to the negative effects of siltation, and suggests that it has been under-recognized on continental shelves elsewhere as a legacy of coastal land use. PMID:28592668

Nineteenth-century collapse of a benthic marine ecosystem on the open continental shelf.

PubMed

Tomašových, Adam; Kidwell, Susan M

2017-06-14

The soft-sediment seafloor of the open continental shelf is among the least-known biomes on Earth, despite its high diversity and importance to fisheries and biogeochemical cycling. Abundant dead shells of epifaunal suspension-feeding terebratulid brachiopods ( Laqueus ) and scallops on the now-muddy mainland continental shelf of southern California reveal the recent, previously unsuspected extirpation of an extensive offshore shell-gravel ecosystem, evidently driven by anthropogenic siltation. Living populations of attached epifauna, which formerly existed in a middle- and outer-shelf mosaic with patches of trophically diverse muds, are restricted today to rocky seafloor along the shelf edge and to the sandier shelves of offshore islands. Geological age-dating of 190 dead brachiopod shells shows that (i) no shells have been produced on the mainland shelf within the last 100 years, (ii) their shell production declined steeply during the nineteenth century, and (iii) they had formerly been present continuously for at least 4 kyr. This loss, sufficiently rapid (less than or equal to 100 years) and thorough to represent an ecosystem collapse, coincides with intensification of alluvial-plain land use in the nineteenth century, particularly livestock grazing. Extirpation was complete by the start of twentieth-century urbanization, warming, bottom fishing and scientific surveys. The loss of this filter-feeding fauna and the new spatial homogeneity and dominance of deposit- and detritus-feeders would have altered ecosystem functioning by reducing habitat heterogeneity and seawater filtering. This discovery, attesting to the power of this geological approach to recent ecological transitions, also strongly increases the spatial scope attributable to the negative effects of siltation, and suggests that it has been under-recognized on continental shelves elsewhere as a legacy of coastal land use. © 2017 The Author(s).

Chydorid Ephippia - a Promising Tool for Climate Reconstruction

NASA Astrophysics Data System (ADS)

Kultti, S.; Sarmaja-Korjonen, K.; Nevalainen, L.

2007-12-01

Ephippium analysis, a recent palaeolimnological method, uses the two reproduction strategies of littoral water fleas of the family Chydoridae (chydorids) to estimate the past length of open-water season in cold-temperate lakes. In northern lakes chydorids reproduce asexually during most of the open-water season until the oncoming winter triggers sexual reproduction. This results in the appearance of males and sexual females, and after fertilization, the formation of a modified female shell (carapace), the ephippium, which protects the resting eggs. Chitinous chydorid remains, including ephippia, preserve well in lake sediments and can be identified to species level. In a mild climate (long open-water season) the period of asexual reproduction is long compared to the period of sexual reproduction, resulting in a higher proportion of shells of asexual females being deposited in sediments than in cold climates where the proportion of ephippia (shells of sexual females) increases. Surface sediment samples were collected from 90 Finnish lakes. The lakes are situated along a transect across Finland where the average open-water season varies from 213 days in the south to 137 days in the north and where annual temperatures vary from +5° C to -2° C, respectively. We tested with statistical methods the relationship between the present ephippium proportions and the present climate normals (1970 - 2000). The preliminary results indicate a clear increase of ephippium proportions from N 60º to N 70º. The linear correlation is highest between ephippium proportion and June temperature (-0.84***). The aim of the study is to provide a model for climate reconstructions on the basis of the analysed data to be applied on past sediments

Crumpled graphene nanoreactors

NASA Astrophysics Data System (ADS)

Wang, Zhongying; Lv, Xiaoshu; Chen, Yantao; Liu, Dan; Xu, Xinhua; Palmore, G. Tayhas R.; Hurt, Robert H.

2015-05-01

Nanoreactors are material structures that provide engineered internal cavities that create unique confined nanoscale environments for chemical reactions. Crumpled graphene nanoparticles or ``nanosacks'' may serve as nanoreactors when filled with reactive or catalytic particles and engineered for a specific chemical function. This article explores the behavior of crumpled graphene nanoreactors containing nanoscale ZnO, Ag, Ni, Cu, Fe, or TiO2 particles, either alone or in combination, in a series of case studies designed to reveal their fundamental behaviors. The first case study shows that ZnO nanoparticles undergo rapid dissolution inside the nanoreactor cavity accompanied by diffusive release of soluble products to surrounding aqueous media through the irregular folded shell. This behavior demonstrates the open nature of the sack structure, which facilitates rapid small-molecule exchange between inside and outside that is a requirement for nanoreactor function. In a case study on copper and silver nanoparticles, encapsulation in graphene nanoreactors is shown in some cases to enhance their oxidation rate in aqueous media, which is attributed to electron transfer from the metal core to graphene that bypasses surface oxides and allows reduction of molecular oxygen on the high-area graphene shell. Nanoreactors also allow particle-particle electron transfer interactions that are mediated by the connecting conductive graphene, which give rise to novel behaviors such as galvanic protection of Ag nanoparticles in Ag/Ni-filled nanoreactors, and the photochemical control of Ag-ion release in Ag/TiO2-filled nanoreactors. It is also shown that internal graphene structures within the sacks provide pockets that reduce particle mobility and inhibit particle sintering during thermal treatment. Finally, these novel behaviors are used to suggest and demonstrate several potential applications for graphene nanoreactors in catalysts, controlled release, and environmental remediation.Nanoreactors are material structures that provide engineered internal cavities that create unique confined nanoscale environments for chemical reactions. Crumpled graphene nanoparticles or ``nanosacks'' may serve as nanoreactors when filled with reactive or catalytic particles and engineered for a specific chemical function. This article explores the behavior of crumpled graphene nanoreactors containing nanoscale ZnO, Ag, Ni, Cu, Fe, or TiO2 particles, either alone or in combination, in a series of case studies designed to reveal their fundamental behaviors. The first case study shows that ZnO nanoparticles undergo rapid dissolution inside the nanoreactor cavity accompanied by diffusive release of soluble products to surrounding aqueous media through the irregular folded shell. This behavior demonstrates the open nature of the sack structure, which facilitates rapid small-molecule exchange between inside and outside that is a requirement for nanoreactor function. In a case study on copper and silver nanoparticles, encapsulation in graphene nanoreactors is shown in some cases to enhance their oxidation rate in aqueous media, which is attributed to electron transfer from the metal core to graphene that bypasses surface oxides and allows reduction of molecular oxygen on the high-area graphene shell. Nanoreactors also allow particle-particle electron transfer interactions that are mediated by the connecting conductive graphene, which give rise to novel behaviors such as galvanic protection of Ag nanoparticles in Ag/Ni-filled nanoreactors, and the photochemical control of Ag-ion release in Ag/TiO2-filled nanoreactors. It is also shown that internal graphene structures within the sacks provide pockets that reduce particle mobility and inhibit particle sintering during thermal treatment. Finally, these novel behaviors are used to suggest and demonstrate several potential applications for graphene nanoreactors in catalysts, controlled release, and environmental remediation. Electronic supplementary information (ESI) available: Fig. S1-S5. See DOI: 10.1039/c5nr00963d

Direct Structural Identification of Gas Induced Gate-Opening Coupled with Commensurate Adsorption in a Microporous Metal-Organic Framework.

PubMed

Banerjee, Debasis; Wang, Hao; Plonka, Anna M; Emge, Thomas J; Parise, John B; Li, Jing

2016-08-08

Gate-opening is a unique and interesting phenomenon commonly observed in flexible porous frameworks, where the pore characteristics and/or crystal structures change in response to external stimuli such as adding or removing guest molecules. For gate-opening that is induced by gas adsorption, the pore-opening pressure often varies for different adsorbate molecules and, thus, can be applied to selectively separate a gas mixture. The detailed understanding of this phenomenon is of fundamental importance to the design of industrially applicable gas-selective sorbents, which remains under investigated due to the lack of direct structural evidence for such systems. We report a mechanistic study of gas-induced gate-opening process of a microporous metal-organic framework, [Mn(ina)2 ] (ina=isonicotinate) associated with commensurate adsorption, by a combination of several analytical techniques including single crystal X-ray diffraction, in situ powder X-ray diffraction coupled with differential scanning calorimetry (XRD-DSC), and gas adsorption-desorption methods. Our study reveals that the pronounced and reversible gate opening/closing phenomena observed in [Mn(ina)2 ] are coupled with a structural transition that involves rotation of the organic linker molecules as a result of interaction of the framework with adsorbed gas molecules including carbon dioxide and propane. The onset pressure to open the gate correlates with the extent of such interaction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local delivery of molecules from a nanopipette for quantitative receptor mapping on live cells.

PubMed

Babakinejad, Babak; Jönsson, Peter; López Córdoba, Ainara; Actis, Paolo; Novak, Pavel; Takahashi, Yasufumi; Shevchuk, Andrew; Anand, Uma; Anand, Praveen; Drews, Anna; Ferrer-Montiel, Antonio; Klenerman, David; Korchev, Yuri E

2013-10-01

Using nanopipettes to locally deliver molecules to the surface of living cells could potentially open up studies of biological processes down to the level of single molecules. However, in order to achieve precise and quantitative local delivery it is essential to be able to determine the amount and distribution of the molecules being delivered. In this work, we investigate how the size of the nanopipette, the magnitude of the applied pressure or voltage, which drives the delivery, and the distance to the underlying surface influences the number and spatial distribution of the delivered molecules. Analytical expressions describing the delivery are derived and compared with the results from finite element simulations and experiments on delivery from a 100 nm nanopipette in bulk solution and to the surface of sensory neurons. We then developed a setup for rapid and quantitative delivery to multiple subcellular areas, delivering the molecule capsaicin to stimulate opening of Transient Receptor Potential Vanilloid subfamily member 1 (TRPV1) channels, membrane receptors involved in pain sensation. Overall, precise and quantitative delivery of molecules from nanopipettes has been demonstrated, opening up many applications in biology such as locally stimulating and mapping receptors on the surface of live cells.

Target electron ionization in Li2+-Li collisions: A multi-electron perspective

NASA Astrophysics Data System (ADS)

Śpiewanowski, M. D.; Gulyás, L.; Horbatsch, M.; Kirchner, T.

2015-05-01

The recent development of the magneto-optical trap reaction-microscope has opened a new chapter for detailed investigations of charged-particle collisions from alkali atoms. It was shown that energy-differential cross sections for ionization from the outer-shell in O8+-Li collisions at 1500 keV/amu can be readily explained with the single-active-electron approximation. Understanding of K-shell ionization, however, requires incorporating many-electron effects. An ionization-excitation process was found to play an important role. We present a theoretical study of target electron removal in Li2+-Li collisions at 2290 keV/amu. The results indicate that in outer-shell ionization a single-electron process plays the dominant part. However, the K-shell ionization results are more difficult to interpret. On one hand, we find only weak contributions from multi-electron processes. On the other hand, a large discrepancy between experimental and single-particle theoretical results indicate that multi-electron processes involving ionization from the outer shell may be important for a complete understanding of the process. Work supported by NSERC, Canada and the Hungarian Scientific Research Fund.

Merging of Kirkendall Growth and Ostwald Ripening: CuO@MnO2 Core-shell Architectures for Asymmetric Supercapacitors

PubMed Central

Huang, Ming; Zhang, Yuxin; Li, Fei; Wang, Zhongchang; Alamusi; Hu, Ning; Wen, Zhiyu; Liu, Qing

2014-01-01

Fabricating hierarchical core-shell nanostructures is currently the subject of intensive research in the electrochemical field owing to the hopes it raises for making efficient electrodes for high-performance supercapacitors. Here, we develop a simple and cost-effective approach to prepare CuO@MnO2 core-shell nanostructures without any surfactants and report their applications as electrodes for supercapacitors. An asymmetric supercapacitor with CuO@MnO2 core-shell nanostructure as the positive electrode and activated microwave exfoliated graphite oxide (MEGO) as the negative electrode yields an energy density of 22.1 Wh kg−1 and a maximum power density of 85.6 kW kg−1; the device shows a long-term cycling stability which retains 101.5% of its initial capacitance even after 10000 cycles. Such a facile strategy to fabricate the hierarchical CuO@MnO2 core-shell nanostructure with significantly improved functionalities opens up a novel avenue to design electrode materials on demand for high-performance supercapacitor applications. PMID:24682149

Two-photon decay of K-shell vacancies in silver atoms

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

Mokler, P.H.; University of Giessen, Giessen; Schaeffer, H.W.

2004-09-01

The spectral distributions for the two-photon decay modes of singly K-shell ionized silver atoms are determined by x-ray-x-ray coincidence measurements. Ag K-shell vacancies were induced by nuclear electron capture decay of radioactive cadmium isotopes {sup 109}Cd and two-photon coincidences were taken back to back (180 deg.) and at a 90 deg. opening angle for the emission. Each of the two-photon transitions from the 2s, 3s, and 3d states exhibits unique angular and spectral distributions. The measurements agree nicely with relativistic self-consistent field calculations of Tong et al. Our results also confirm and extend the earlier experimental data of Ilakovac andmore » co-workers with improved accuracy.« less

Intracellular responsive dual delivery by endosomolytic polyplexes carrying DNA anchored porous silicon nanoparticles.

PubMed

Shahbazi, Mohammad-Ali; Almeida, Patrick Vingadas; Correia, Alexandra; Herranz-Blanco, Barbara; Shrestha, Neha; Mäkilä, Ermei; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A

2017-03-10

Bioresponsive cytosolic nanobased multidelivery has been emerging as an enormously challenging novel concept due to the intrinsic protective barriers of the cells and hardly controllable performances of nanomaterials. Here, we present a new paradigm to advance nano-in-nano integration technology amenable to create multifunctional nanovehicles showing considerable promise to overcome restrictions of intracellular delivery, solve impediments of endosomal localization and aid effectual tracking of nanoparticles. A redox responsive intercalator chemistry comprised of cystine and 9-aminoacridine is designed as a cross-linker to cap carboxylated porous silicon nanoparticles with DNA. These intelligent nanocarriers are then encapsulated within novel one-pot electrostatically complexed nano-networks made of a zwitterionic amino acid (cysteine), an anionic bioadhesive polymer (poly(methyl vinyl ether-alt-maleic acid)) and a cationic endosomolytic polymer (polyethyleneimine). This combined nanocomposite is successfully tested for the co-delivery of hydrophobic (sorafenib) or hydrophilic (calcein) molecules loaded within the porous core, and an imaging agent covalently integrated into the polyplex shell by click chemistry. High loading capacity, low cyto- and hemo-toxicity, glutathione responsive on-command drug release, and superior cytosolic delivery are shown as achievable key features of the proposed formulation. Overall, formulating drug molecules, DNA and imaging agents, without any interference, in a physico-chemically optimized carrier may open a path towards broad applicability of these cost-effective multivalent nanocomposites for treating different diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Desert Tortoise Head-start Program at Twentynine Palms Marine Base

DTIC Science & Technology

2013-04-02

Hillard. Shell hardness measurement in juvenile desert tortoises, Gopherus agassizii, Herpetological Review, (09 2011): 0. doi: 07/23/2012 2.00...yearlings released to the open desert. Herpetological Conservation and Biology.

Cylindrical Shells Made of Stainless Steel - Investigation of Postbuckling

NASA Astrophysics Data System (ADS)

Stehr, Sebastian; Stranghöner, Natalie

2017-06-01

The relevant load case of open thin-walled shells is often wind loading during construction. Because of the missing stabilization effect of the roof they show a very high sensitivity to buckling which results into higher wall thicknesses. As part of the European RFCS research project BiogaSS the Institute for Metal and Lightweight Structures of the University of Duisburg-Essen carried out investigations on open thin-walled tanks made of austenitic and duplex stainless steels under wind load to study a possible economic advantage which might be gained from the consideration of the elastic postbuckling behaviour. This contribution presents not only experimental and numerical results but also first recommendations regarding the range of possible buckling reduction factors which might be incorporated in future revisions of EN 1993-1-6 and EN 1993-4-2.

Improving the sensitivity of immunoassay based on MBA-embedded Au@SiO2 nanoparticles and surface enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wei, Chao; Xu, Min-Min; Fang, Cong-Wei; Jin, Qi; Yuan, Ya-Xian; Yao, Jian-Lin

2017-03-01

Traditional "sandwich" structure immunoassay is mainly based on the self-assembly of "antibody on solid substrate-antigen-antibody with nanotags" architectures, and the sensitivity of this strategy is critically depended on the surface enhanced Raman scattering (SERS) activities and stability of nanotags. Therefore, the rational design and fabrication on the SERS nanotags attracts the common interests to the bio-related detecting and imaging. Herein, silica encapsulated Au with mercaptobenzoic acid (MBA) core-shell nanoparticles (Au-MBA@SiO2) are fabricated instead of the traditional naked Au or Ag nanoparticles for the SERS-based immunoassay on human and mouse IgG antigens. The MBA molecules facilitate the formation of continuous pinhole-free silica shell and are also used as SERS labels. The silica shell is employed to protect MBA labels and to isolate Au core from the ambient solution for blocking the aggregation. This shell also played the similar role to BSA in inhibiting the nonspecific bindings, which allowed the procedures for constructing "sandwich" structures to be simplified. All of these merits of the Au-MBA@SiO2 brought the high performance in the related immunoassay. Benefiting from the introduction of silica shell to encapsulate MBA labels, the detection sensitivity was improved by about 1- 2 orders of magnitude by comparing with the traditional approach based on naked Au-MBA nanoparticles. This kind of label-embedded core-shell nanoparticles could be developed as the versatile nanotags for the bioanalysis and bioimaging.

Radial direct bandgap p-i-n GaNP microwire solar cells with enhanced short circuit current

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

Sukrittanon, Supanee; Liu, Ren; Pan, Janet L.

2016-08-07

We report the demonstration of dilute nitride heterostructure core/shell microwire solar cells utilizing the combination of top-down reactive-ion etching to create the cores (GaP) and molecular beam epitaxy to create the shells (GaNP). Systematic studies of cell performance over a series of microwire lengths, array periods, and microwire sidewall morphologies examined by transmission electron microscopy were conducted to shed light on performance-limiting factors and to optimize the cell efficiency. We show by microscopy and correlated external quantum efficiency characterization that the open circuit voltage is degraded primarily due to the presence of defects at the GaP/GaNP interface and in themore » GaNP shells, and is not limited by surface recombination. Compared to thin film solar cells in the same growth run, the microwire solar cells exhibit greater short circuit current but poorer open circuit voltage due to greater light absorption and number of defects in the microwire structure, respectively. The comprehensive understanding presented in this work suggests that performance benefits of dilute nitride microwire solar cells can be achieved by further tuning of the epitaxial quality of the underlying materials.« less

Evaluating and interpreting the chemical relevance of the linear response kernel for atoms II: open shell.

PubMed

Boisdenghien, Zino; Fias, Stijn; Van Alsenoy, Christian; De Proft, Frank; Geerlings, Paul

2014-07-28

Most of the work done on the linear response kernel χ(r,r') has focussed on its atom-atom condensed form χAB. Our previous work [Boisdenghien et al., J. Chem. Theory Comput., 2013, 9, 1007] was the first effort to truly focus on the non-condensed form of this function for closed (sub)shell atoms in a systematic fashion. In this work, we extend our method to the open shell case. To simplify the plotting of our results, we average our results to a symmetrical quantity χ(r,r'). This allows us to plot the linear response kernel for all elements up to and including argon and to investigate the periodicity throughout the first three rows in the periodic table and in the different representations of χ(r,r'). Within the context of Spin Polarized Conceptual Density Functional Theory, the first two-dimensional plots of spin polarized linear response functions are presented and commented on for some selected cases on the basis of the atomic ground state electronic configurations. Using the relation between the linear response kernel and the polarizability we compare the values of the polarizability tensor calculated using our method to high-level values.

Radial direct bandgap p-i-n GaNP microwire solar cells with enhanced short circuit current

NASA Astrophysics Data System (ADS)

Sukrittanon, Supanee; Liu, Ren; Breeden, Michael C.; Pan, Janet L.; Jungjohann, K. L.; Tu, Charles W.; Dayeh, Shadi A.

2016-08-01

We report the demonstration of dilute nitride heterostructure core/shell microwire solar cells utilizing the combination of top-down reactive-ion etching to create the cores (GaP) and molecular beam epitaxy to create the shells (GaNP). Systematic studies of cell performance over a series of microwire lengths, array periods, and microwire sidewall morphologies examined by transmission electron microscopy were conducted to shed light on performance-limiting factors and to optimize the cell efficiency. We show by microscopy and correlated external quantum efficiency characterization that the open circuit voltage is degraded primarily due to the presence of defects at the GaP/GaNP interface and in the GaNP shells, and is not limited by surface recombination. Compared to thin film solar cells in the same growth run, the microwire solar cells exhibit greater short circuit current but poorer open circuit voltage due to greater light absorption and number of defects in the microwire structure, respectively. The comprehensive understanding presented in this work suggests that performance benefits of dilute nitride microwire solar cells can be achieved by further tuning of the epitaxial quality of the underlying materials.

Radial direct bandgap p-i-n GaNP microwire solar cells with enhanced short circuit current

DOE PAGES

Sukrittanon, Supanee; Liu, Ren; Breeden, Michael C.; ...

2016-08-07

Here, we report the demonstration of dilute nitride heterostructure core/shell microwire solar cells utilizing the combination of top-down reactive-ion etching to create the cores (GaP) and molecular beam epitaxy to create the shells (GaNP). Systematic studies of cell performance over a series of microwire lengths, array periods, and microwire sidewall morphologies examined by transmission electron microscopy were conducted to shed light on performance-limiting factors and to optimize the cell efficiency. We also show by microscopy and correlated external quantum efficiency characterization that the open circuit voltage is degraded primarily due to the presence of defects at the GaP/GaNP interface andmore » in the GaNP shells, and is not limited by surface recombination. Compared to thin film solar cells in the same growth run, the microwire solar cells exhibit greater short circuit current but poorer open circuit voltage due to greater light absorption and number of defects in the microwire structure, respectively. Finally, we present performance benefits of dilute nitride microwire solar cells and show that it can be achieved by further tuning of the epitaxial quality of the underlying materials.« less

Structural fluctuation governed dynamic diradical character in pentacene.

PubMed

Yang, Hongfang; Chen, Mengzhen; Song, Xinyu; Bu, Yuxiang

2015-06-07

We unravel intriguing dynamical diradical behavior governed by structural fluctuation in pentacene using ab initio molecular dynamics simulation. In contrast to static equilibrium configuration of pentacene with a closed-shell ground state without diradical character, due to structural fluctuation, some of its dynamical snapshot configurations exhibit an open-shell broken-symmetry singlet ground state with diradical character, and such diradical character presents irregular pulsing behavior in time evolution. Not all structural changes can lead to diradical character, only those involving the shortening of cross-linking C-C bonds and variations of the C-C bonds in polyacetylene chains are the main contributors. This scenario about diradicalization is distinctly different from that in long acenes. The essence is that structural distortion cooperatively raises the HOMO and lowers the LUMO, efficiently reducing the HOMO-LUMO and singlet-triplet energy gaps, which facilitate the formation of a broken-symmetry open-shell singlet state. The irregular pulsing behavior originates from the mixing of normal vibrations in pentacene. This fascinating behavior suggests the potential application of pentacene as a suitable building block in the design of new electronic devices due to its magnetism-controllability through energy induction. This work provides new insight into inherent electronic property fluctuation in acenes.

Global solutions of restricted open-shell Hartree-Fock theory from semidefinite programming with applications to strongly correlated quantum systems.

PubMed

Veeraraghavan, Srikant; Mazziotti, David A

2014-03-28

We present a density matrix approach for computing global solutions of restricted open-shell Hartree-Fock theory, based on semidefinite programming (SDP), that gives upper and lower bounds on the Hartree-Fock energy of quantum systems. While wave function approaches to Hartree-Fock theory yield an upper bound to the Hartree-Fock energy, we derive a semidefinite relaxation of Hartree-Fock theory that yields a rigorous lower bound on the Hartree-Fock energy. We also develop an upper-bound algorithm in which Hartree-Fock theory is cast as a SDP with a nonconvex constraint on the rank of the matrix variable. Equality of the upper- and lower-bound energies guarantees that the computed solution is the globally optimal solution of Hartree-Fock theory. The work extends a previously presented method for closed-shell systems [S. Veeraraghavan and D. A. Mazziotti, Phys. Rev. A 89, 010502-R (2014)]. For strongly correlated systems the SDP approach provides an alternative to the locally optimized Hartree-Fock energies and densities with a certificate of global optimality. Applications are made to the potential energy curves of C2, CN, Cr2, and NO2.

Plasmonic nanostructures for surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Jiang, Ruiqian

In the last three decades, a large number of different plasmonic nanostructures have attracted much attention due to their unique optical properties. Those plasmonic nanostructures include nanoparticles, nanoholes and metal nanovoids. They have been widely utilized in optical devices and sensors. When the plasmonic nanostructures interact with the electromagnetic wave and their surface plasmon frequency match with the light frequency, the electrons in plasmonic nanostructures will resonate with the same oscillation as incident light. In this case, the plasmonic nanostructures can absorb light and enhance the light scattering. Therefore, the plasmonic nanostructures can be used as substrate for surface-enhanced Raman spectroscopy to enhance the Raman signal. Using plasmonic nanostructures can significantly enhance Raman scattering of molecules with very low concentrations. In this thesis, two different plasmonic nanostructures Ag dendrites and Au/Ag core-shell nanoparticles are investigated. Simple methods were used to produce these two plasmonic nanostructures. Then, their applications in surface enhanced Raman scattering have been explored. Ag dendrites were produced by galvanic replacement reaction, which was conducted using Ag nitrate aqueous solution and copper metal. Metal copper layer was deposited at the bottom side of anodic aluminum oxide (AAO) membrane. Silver wires formed inside AAO channels connected Ag nitrate on the top of AAO membrane and copper layer at the bottom side of AAO. Silver dendrites were formed on the top side of AAO. The second plasmonic nanostructure is Au/Ag core-shell nanoparticles. They were fabricated by electroless plating (galvanic replacement) reaction in a silver plating solution. First, electrochemically evolved hydrogen bubbles were used as template through electroless deposition to produce hollow Au nanoparticles. Then, the Au nanoparticles were coated with Cu shells in a Cu plating solution. In the following step, a AgCN based plating solution was used to replace Cu shell to form Au/Ag core-shell nanoparticles. These two plasmonic nanostructures were tested as substrates for Raman spectroscopy. It demonstrated that these plasmonic nanostructures could enhance Raman signal from the molecules on their surface. The results indicate that these plasmonic nanostructures could be utilized in many fields, such as such as biological and environmental sensors.

Mechanical properties, microstructure, and specific adhesion of phospholipid monolayer-coated microbubbles

NASA Astrophysics Data System (ADS)

Kim, Dennis Heejong

1999-10-01

The objective of this study was to characterize properties of phospholipid monolayer shells formed on gas microbubbles, specifically (1)yield shear and shear viscosity as a function of the shell composition, (2)yield shear, shear viscosity, and microstructural domain density as a function of the quenching rate of the microbubbles following production, and (3)the adhesion of a lipid-coated microbubble to a colloidal substrate via receptor-ligand mediated specific interaction, either enhanced or inhibited by the presence of surface-grafted polymeric structures. The primary experimental technique employed was the micromanipulation method, wherein tapered fluid-filled pipets with bores on the order of 4-10 microns were used to (1)capture and maneuver individual micron scale bubbles in aqueous medium, and (2)apply suction pressures over the range of 1 dyn cm-2 to 10 5 dyn cm-2 (10-6 to 10 -1 atm) and track the corresponding deformation of the microbubble under applied pressure. The yield shear and shear viscosity increase with increasing acyl chain length of the lipid; an equivalent statement is that the yield shear and shear viscosity increase with reduced temperature of the shell material. Crystalline lipid domain sizes are dictated by the rate at which the system is (temperature) quenched in a manner predicted by classic materials science and metallurgy: rapidly cooled samples form the smallest grains and exhibit the lowest levels of yield shear and shear viscosity. Slowly cooled samples produce large grains and exhibit high levels of yield and viscosity. The success and strength of adhesion of a microbubble to a substrate is dictated by the identity of the adhesive molecules participating in the adhesion, as well as the surface architecture of the interfaces participating in adhesion. The term surface architecture is used to describe the physical arrangement of the full complement of steric stabilizers, spacers, and binding molecules present at the surface of a typical coated microbubble shell. Adhesion is successful for systems where the binding ligand is not impeded by the presence of surface-grafted poly(ethylene glycol) (PEG) moieties. Like the shell composition itself, the surface construct can be engineered to produce optimal performance in adhesion.

Adsorption of insulin peptide on charged single-walled carbon nanotubes: significant role of ordered water molecules.

PubMed

Shen, Jia-Wei; Wu, Tao; Wang, Qi; Kang, Yu; Chen, Xin

2009-06-02

Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems [picture: see text], but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction.Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein-CNT complexes by charging the CNTs.

Ancient DNA analysis identifies marine mollusc shells as new metagenomic archives of the past.

PubMed

Der Sarkissian, Clio; Pichereau, Vianney; Dupont, Catherine; Ilsøe, Peter C; Perrigault, Mickael; Butler, Paul; Chauvaud, Laurent; Eiríksson, Jón; Scourse, James; Paillard, Christine; Orlando, Ludovic

2017-09-01

Marine mollusc shells enclose a wealth of information on coastal organisms and their environment. Their life history traits as well as (palaeo-) environmental conditions, including temperature, food availability, salinity and pollution, can be traced through the analysis of their shell (micro-) structure and biogeochemical composition. Adding to this list, the DNA entrapped in shell carbonate biominerals potentially offers a novel and complementary proxy both for reconstructing palaeoenvironments and tracking mollusc evolutionary trajectories. Here, we assess this potential by applying DNA extraction, high-throughput shotgun DNA sequencing and metagenomic analyses to marine mollusc shells spanning the last ~7,000 years. We report successful DNA extraction from shells, including a variety of ancient specimens, and find that DNA recovery is highly dependent on their biomineral structure, carbonate layer preservation and disease state. We demonstrate positive taxonomic identification of mollusc species using a combination of mitochondrial DNA genomes, barcodes, genome-scale data and metagenomic approaches. We also find shell biominerals to contain a diversity of microbial DNA from the marine environment. Finally, we reconstruct genomic sequences of organisms closely related to the Vibrio tapetis bacteria from Manila clam shells previously diagnosed with Brown Ring Disease. Our results reveal marine mollusc shells as novel genetic archives of the past, which opens new perspectives in ancient DNA research, with the potential to reconstruct the evolutionary history of molluscs, microbial communities and pathogens in the face of environmental changes. Other future applications include conservation of endangered mollusc species and aquaculture management. © 2017 John Wiley & Sons Ltd.

Evaluation of columns packed with shell particles with compounds of pharmaceutical interest.

PubMed

Ruta, Joséphine; Zurlino, Daria; Grivel, Candice; Heinisch, Sabine; Veuthey, Jean-Luc; Guillarme, Davy

2012-03-09

The commercial C18 columns packed with sub-3 μm shell particles were tested and compared to a reference UHPLC column, in terms of kinetic performance as well as selectivity, retention capability, peak shape and loading capacity. For this purpose, a set of pharmaceutically relevant molecules was selected, including acidic, neutral and basic drugs. Regarding kinetic performance, h(opt) values for the shell particles were found between 1.7 and 2, while the UHPLC column provided a value of approximately 2.5. However, this impressive performance should be considered with caution, particularly for the construction of kinetic plots since h(opt) values were sometimes related to the column dimensions, depending on the provider (h(opt) comprised between 1.8 and 2.6 for longer columns of 150 mm packed with shell particles). Despite the non-porous inner core of the shell particles representing between 25 and 36% of the particle, we demonstrated that the decrease in retention was on the maximum equal to 15% for Ascentis column while Acquity and Poroshell were strictly equivalent in terms of retention. Concerning loading capacity, it remains comparable to that of fully porous sub-2 μm particles and always more pronounced with 0.1% formic acid vs. phosphate buffer. The loading capacity of the different columns was found to be better correlated to the pore volume or surface coverage than the shell thickness. Experimentally, the most pronounced overloading was observed with the Poroshell. Finally, the selectivity and peak shape were evaluated using a mixture of basic and acidic drugs. It appears that results were very similar between sub-3 μm shell particles and fully porous sub-2-μm particles for our mixture of compounds, showing the ability to transfer existing methods to shell particles, with only limited adjustments. This study confirms the potential of columns packed with shell particles and demonstrates the interest of such column technology with pharmaceutical compounds. Copyright © 2011 Elsevier B.V. All rights reserved.

Rigid removable cover for dorsal wound protection and tube fixation in pigs.

PubMed

Stynes, G D; Kiroff, G K; Morrison, W A; Edwards, G A; Page, R S; Kirkland, M A

2016-04-01

To report the design and benefits of a rigid polyethylene cover 'shell' for the protection of dorsal torso wounds and tube fixation in pigs. Open C-shaped polyethylene shells were designed to protect wounds and dressings on the dorsum of pigs used in research into negative pressure dressing-assisted wound healing. The shells were designed to resist trauma and contamination, to be comfortable and expansible, and to facilitate tube fixation and management. Strap fixation was optimised during experimentation. Efficacy was assessed by direct observation of dressing and wound protection, tube integrity and by macroscopic and microscopic assessments of wound healing. The shells effectively protected the wounds against blunt and sharp trauma, were simple to remove and reapply, were well tolerated and allowed for growth of the pigs. Circumferential neck straps attached by lateral straps to the shells proved critical. There was no wound infection or inflammation underlying the shells. Porting tubing via mid-dorsal holes in the shells and affixing the tubing just cranial to these holes prevented tube damage and traction, permitted tube management from outside the cages and allowed the pigs to move freely without becoming entangled. These shells effectively protected dorsal skin wounds and dressings, prevented tube damage and facilitated tube management in pigs. Similar systems may be useful for other production animals for wound management and for tube management with negative pressure wound healing, drain tubes or the delivery of nutrition, fluids or medications. © 2016 Australian Veterinary Association.

Modular heat exchanger

DOEpatents

Giardina, A.R.

1981-03-03

A shell and tube heat exchanger is described having a plurality of individually removable tube bundle modules. A lattice of structural steel forming rectangular openings therein is placed at each end of a cylindrical shell. Longitudinal structural members are placed in the shell between corners of the rectangular openings situated on opposite ends of the shell. Intermediate support members interconnect the longitudinal supports so as to increase the longitudinal supports rigidity. Rectangular parallelepiped tube bundle modules occupy the space defined by the longitudinal supports and end supports and each include a rectangular tube sheet situated on each end of a plurality of tubes extending there through, a plurality of rectangular tube supports located between the tube sheets, and a tube bundle module stiffening structure disposed about the bundle's periphery and being attached to the tube sheets and tube supports. The corners of each tube bundle module have longitudinal framework members which are mateable with and supported by the longitudinal support members. Intermediate support members constitute several lattices, each of which is situated in a plane between the end support members. The intermediate support members constituting the several lattices extend horizontally and vertically between longitudinal supports of adjacent tube module voids. An alternative embodiment for intermediate support members constitute a series of structural plates situated at the corners of the module voids and having recesses therein for receiving the respective longitudinal support members adjacent thereto, protrusions separating the recesses, and a plurality of struts situated between protrusions of adjacent structural plates. 12 figs.

Modular heat exchanger

DOEpatents

Giardina, Angelo R. [Marple Township, Delaware County, PA

1981-03-03

A shell and tube heat exchanger having a plurality of individually removable tube bundle modules. A lattice of structural steel forming rectangular openings therein is placed at each end of a cylindrical shell. Longitudinal structural members are placed in the shell between corners of the rectangular openings situated on opposite ends of the shell. Intermediate support members interconnect the longitudinal supports so as to increase the longitudinal supports rigidity. Rectangular parallelpiped tube bundle moldules occupy the space defined by the longitudinal supports and end supports and each include a rectangular tube sheet situated on each end of a plurality of tubes extending therethrough, a plurality of rectangular tube supports located between the tube sheets, and a tube bundle module stiffening structure disposed about the bundle's periphery and being attached to the tube sheets and tube supports. The corners of each tube bundle module have longitudinal framework members which are mateable with and supported by the longitudinal support members. Intermediate support members constitute several lattice, each of which is situate d in a plane between the end support members. The intermediate support members constituting the several lattice extend horizontally and vertically between longitudinal supports of adjacent tube module voids. An alternative embodiment for intermediate support members constitute a series of structural plates situated at the corners of the module voids and having recesses therein for receiving the respective longitudinal support members adjacent thereto, protrusions separating the recesses, and a plurality of struts situated between protrusions of adjacent structural plates.

Electrochemical Properties of Boron-Doped Fullerene Derivatives for Lithium-Ion Battery Applications.

PubMed

Sood, Parveen; Kim, Ki Chul; Jang, Seung Soon

2018-03-19

The high electron affinity of fullerene C 60 coupled with the rich chemistry of carbon makes it a promising material for cathode applications in lithium-ion batteries. Since boron has one electron less than carbon, the presence of boron on C 60 cages is expected to generate electron deficiency in C 60 , and thereby to enhance its electron affinity. By using density functional theory (DFT), we studied the redox potentials and electronic properties of C 60 and C 59 B. We have found that doping C 60 with one boron atom results in a substantial increase in redox potential from 2.462 V to 3.709 V, which was attributed to the formation of an open shell system. We also investigated the redox and electronic properties of C 59 B functionalized with various redox-active oxygen containing functional groups (OCFGs). For the combination of functionalization with OCFGs and boron doping, it is found that the enhancement of redox potential is reduced, which is mainly attributed to the open shell structure being changed to a closed-shell one. Nevertheless, the redox potentials are still higher than that of pristine C 60 . From the observation that the lowest unoccupied molecular orbital of closed-shell OCFG- functionalized C 59 B is correlated well with the redox potential, it was confirmed that the spin state is crucial to be considered to understand the relationship between electronic structure and redox properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

PubMed

Wen, Bao-Ying; Jin, Xi; Li, Yue; Wang, Ya-Hao; Li, Chao-Yu; Liang, Miao-Miao; Panneerselvam, Rajapandiyan; Xu, Qing-Chi; Wu, De-Yin; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2016-06-21

For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data.

Evidence for Reduced Hydrogen-Bond Cooperativity in Ionic Solvation Shells from Isotope-Dependent Dielectric Relaxation

NASA Astrophysics Data System (ADS)

Cota, Roberto; Ottosson, Niklas; Bakker, Huib J.; Woutersen, Sander

2018-05-01

We find that the reduction in dielectric response (depolarization) of water caused by solvated ions is different for H2O and D2O . This isotope dependence allows us to reliably determine the kinetic contribution to the depolarization, which is found to be significantly smaller than predicted by existing theory. The discrepancy can be explained from a reduced hydrogen-bond cooperativity in the solvation shell: we obtain quantitative agreement between theory and experiment by reducing the Kirkwood correlation factor of the solvating water from 2.7 (the bulk value) to ˜1.6 for NaCl and ˜1 (corresponding to completely uncorrelated motion of water molecules) for CsCl.

Molecular dynamics study of the solvation of calcium carbonate in water.

PubMed

Bruneval, Fabien; Donadio, Davide; Parrinello, Michele

2007-10-25

We performed molecular dynamics simulations of diluted solutions of calcium carbonate in water. To this end, we combined and tested previous polarizable models. The carbonate anion forms long-living hydrogen bonds with water and shows an amphiphilic character, in which the water molecules are expelled in a region close to its C(3) symmetry axis. The calcium cation forms a strongly bound ion pair with the carbonate. The first hydration shell around the CaCO(3) pair is found to be very similar to the location of the water molecules surrounding CaCO(3) in ikaite, the hydrated mineral.

7 CFR 51.1442 - Piece.

Code of Federal Regulations, 2010 CFR

2010-01-01

... Standards for Grades of Shelled Pecans Definitions § 51.1442 Piece. Piece means a portion of a kernel which is less than seven-eighths of a half-kernel, but which will not pass through a round opening two...

24. Historic American Buildings Survey E. W. Russell, Photographer, May ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

24. Historic American Buildings Survey E. W. Russell, Photographer, May 7, 1936 N. DOOR OPENING ON PORTICO (OR ARCADE) - Spring Hill College, Main Building, Old Shell Road, Spring Hill, Mobile County, AL

Open conformers: the hidden face of MHC-I molecules.

PubMed

Arosa, Fernando A; Santos, Susana G; Powis, Simon J

2007-03-01

A pool of MHC-I molecules present at the plasma membrane can dissociate from the peptide and/or the light chain, becoming open MHC-I conformers. Whereas peptide-bound MHC-I molecules have an important role in regulating adaptive and innate immune responses, through trans-interactions with T cell and NK cell receptors, the function of the open MHC-I conformers is less clear but seems to be related to their inherent ability to cis-associate, both with themselves and with other receptors. Here, we review data indicating the open MHC-I conformers as regulators of ligand-receptor interactions and discuss the biological implications for immune and non-immune cells. The likelihood that the MHC-I heavy chains have hidden functions that are determined by the amino acid sequence of the alpha1 and alpha2 domains are discussed.

Miscibility at the immiscible liquid/liquid interface: A molecular dynamics study of thermodynamics and mechanism

NASA Astrophysics Data System (ADS)

Karnes, John J.; Benjamin, Ilan

2018-01-01

Molecular dynamics simulations are used to study the dissolution of water into an adjacent, immiscible organic liquid phase. Equilibrium thermodynamic and structural properties are calculated during the transfer of water molecule(s) across the interface using umbrella sampling. The net free energy of transfer agrees reasonably well with experimental solubility values. We find that water molecules "prefer" to transfer into the adjacent phase one-at-a-time, without co-transfer of the hydration shell, as in the case of evaporation. To study the dynamics and mechanism of transfer of water to liquid nitrobenzene, we collected over 400 independent dissolution events. Analysis of these trajectories suggests that the transfer of water is facilitated by interfacial protrusions of the water phase into the organic phase, where one water molecule at the tip of the protrusion enters the organic phase by the breakup of a single hydrogen bond.

[Spectroscopic Study of Salbutamol Molecularly Imprinted Polymers].

PubMed

Ren, Hui-peng; Guan, Yu-yu; Dai, Rong-hua; Liu, Guo-yan; Chai, Chun-yan

2016-02-01

In order to solve the problem of on-site rapid detection of salbutamol residues in feed and animal products, and develop a new method of fast detection of salbutamol on the basis of the molecular imprinting technology, this article uses the salbutamol (SAL) working as template molecule, methacrylic acid (MAA) working as functional monomer. On this basis, a new type of core-shell type salbutamol molecularly imprinted polymers were prepared with colloidal gold particles as triggering core. Superficial characteristics of the MIPs and the related compounds were investigated by ultraviolet (UV) spectra and infrared (IR) spectra, Raman spectra, Scanning electron microscopy (SEM) respectively. The results indicated that a stable hydrogen bonding complex has been formed between the carboxyl groups of SAL and MA with a matching ratio of 1:1. The complex can be easily eluted by the reagent containing hydrogen bonding. The chemical binding constant K reaches -0.245 x 10⁶ L² · mol⁻². The possible binding sites of the hydrogen bonding was formed between the hydrogen atoms of -COOH in MA and the oxygen atoms of C==O in SAL. IR and Raman spectrum showed that, compared with MA, a significant red shift of -OH absorption peak was manifested in MIPs, which proved that SAL as template molecule occurred a specific bond between MA. Red shift of stretching vibration absorption peak of C==O was also detected in the un-eluted MIPs and obvious energy loss happened, which demonstrated a possible binding sites is SAL intramolecular of C==O atom of oxygen. If the hydrogen atoms of -COOH in MA wanted to generate hydrogen bond. However, the shapes of absorption peak of other functional groups including C==C, C==O, and -OH were very similar both in MIPs and NIPs. Specific cavities were formed after the template molecules in MIPs were removed. It was proved by the adsorption experiment that the specific sites in these cavities highly match with the chemical and space structure of SAL. Besides, colloidal gold type core-shell molecularly imprinted polymers have looser surface, more cavities in the surface compared with ordinary molecularly imprinted polymers, which increased the effective area of adsorption to target molecules. So it have better performance in adsorption. Based on the principle that these cavities can specificly recognize and combine with target molecule in the test sample, and the excellent ability of colloidal gold core-shell molecularly imprinted polymers, the development of novel methods for fast determination of SAL based on the molecular imprinting technology can be expected in the near future.

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

Mumin, Md Abdul, E-mail: pcharpentier@eng.uwo.ca; Akhter, Kazi Farida, E-mail: pcharpentier@eng.uwo.ca; Charpentier, Paul A., E-mail: pcharpentier@eng.uwo.ca

Semiconductor nanocrystals (NCs) (also known as quantum dots, QDs) have attracted immense attention for their size-tunable optical properties that makes them impressive candidates for solar cells, light emitting devices, lasers, as well as biomedical imaging. However monodispersity, high and consistent photoluminescence, photostability, and biocompatibility are still major challenges. This work focuses on optimizing the photophysical properties and biocompatibility of QDs by forming core-shell nanostructures and their encapsulation by a carrier. Highly luminescent CdS and CdS-ZnS core-shell QDs with 5 nm sizes were synthesized using a facile approach based on pyrolysis of the single molecule precursors. After capping the CdS QDsmore » with a thin layer of ZnS to reduce toxicity, the photoluminescence and photostability of the core-shell QDs was significantly enhanced. To make both the bare and core/shell structure QDs more resistant against photochemical reactions, a mesoporous silica layer was grown on the QDs through a reverse microemulsion technique based on hydrophobic interaction. This encapsulation enhanced the quantum yield and photostability compared to the bare QDs by providing much stronger resistance to oxidation and Oswald ripening of QDs. Encapsulation also improved biocompatibility of QDs that was evaluated with human umbilical vein endothelial cell lines (HUVEC)« less

Fluorescent nanodiamonds embedded in biocompatible translucent shells.

PubMed

Rehor, Ivan; Slegerova, Jitka; Kucka, Jan; Proks, Vladimir; Petrakova, Vladimira; Adam, Marie-Pierre; Treussart, François; Turner, Stuart; Bals, Sara; Sacha, Pavel; Ledvina, Miroslav; Wen, Amy M; Steinmetz, Nicole F; Cigler, Petr

2014-03-26

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio-orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30-nm fluorescent nanodiamonds (FNDs) in 10-20-nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near-spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio-orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells

PubMed Central

Rehor, Ivan; Slegerova, Jitka; Kucka, Jan; Proks, Vladimir; Petrakova, Vladimira; Adam, Marie-Pierre; Treussart, François; Turner, Stuart; Bals, Sara; Sacha, Pavel; Ledvina, Miroslav; Wen, Amy M.; Steinmetz, Nicole F.; Cigler, Petr

2016-01-01

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio-orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30-nm fluorescent nanodiamonds (FNDs) in 10–20-nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near-spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio-orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells. PMID:24500945

On demand manufacturing of patient-specific liquid capsules via co-ordinated 3D printing and liquid dispensing.

PubMed

Okwuosa, Tochukwu C; Soares, Cindy; Gollwitzer, Verena; Habashy, Rober; Timmins, Peter; Alhnan, Mohamed A

2018-06-15

A method for the production of liquid capsules with the potential of modifying drug dose and release is presented. For the first time, the co-ordinated use of fused deposition modelling (FDM), 3D printing and liquid dispensing to fabricate individualised dosage form on demand in a fully automated fashion has been demonstrated. Polymethacrylate shells (Eudragit EPO and RL) for immediate and extended release were fabricated using FDM 3D printing and simultaneously filled using a computer-controlled liquid dispenser loaded with model drug solution (theophylline) or suspension (dipyridamole). The impact of printing modes: simultaneous shell printing and filling (single-phase) or sequential 3D printing of shell bottom, filling and shell cap (multi-phase), nozzle size, syringe volume, and shell structure has been reported. The use of shell thickness of 1.6 mm, and concentric architecture allowed successful containment of liquid core whilst maintaining the release properties of the 3D printed liquid capsule. The linear relationship between the theoretical and the actual volumes from the dispenser reflected its potential for accurate dosing (R 2  = 0.9985). Modifying the shell thickness of Eudragit RL capsule allowed a controlled extended drug release without the need for formulation change. Owing to its low cost and versatility, this approach can be adapted to wide spectrum of liquid formulations such as small and large molecule solutions and obviate the need for compatibility with the high temperature of FDM 3D printing process. In a clinical setting, health care staff will be able to instantly manufacture in small volumes liquid capsules with individualised dose contents and release pattern in response to specific patient's needs. Copyright © 2018 Elsevier B.V. All rights reserved.

Comparative study of new shell-type, sub-2 micron fully porous and monolith stationary phases, focusing on mass-transfer resistance.

PubMed

Oláh, Erzsébet; Fekete, Szabolcs; Fekete, Jeno; Ganzler, Katalin

2010-06-04

Today sub-2 microm packed columns are very popular to conduct fast chromatographic separations. The mass-transfer resistance depends on the particle size but some practical limits exist not to reach the theoretically expected plate height and mass-transfer resistance. Another approach applies particles with shortened diffusion path to enhance the efficiency of separations. In this study a systematical evaluation of the possibilities of the separations obtained with 5 cm long narrow bore columns packed with new 2.6 microm shell particles (1.9 microm nonporous core surrounded by a 0.35 microm porous shell, Kinetex, Core-Shell), packed with other shell-type particles (Ascentis Express, Fused-Core), totally porous sub-2 microm particles and a 5 cm long narrow bore monolith column is presented. The different commercially available columns were compared by using van Deemter, Knox and kinetic plots. Theoretical Poppe plots were constructed for each column to compare their kinetic performance. Data are presented on polar neutral real-life analytes. Comparison of a low molecular weight compounds (MW=270-430) and a high molecular weight one (MW approximately 900) was conducted. This study proves that the Kinetex column packed with 2.6 microm shell particles is worthy of rivaling to sub-2 microm columns and other commercially available shell-type packings (Ascentis Express or Halo), both for small and large molecule separation. The Kinetex column offers a very flat C term. Utilizing this feature, high flow rates can be applied to accomplish very fast separations without significant loss in efficiency. Copyright 2010 Elsevier B.V. All rights reserved.

High-Performance Core–Shell Catalyst with Nitride Nanoparticles as a Core: Well-Defined Titanium Copper Nitride Coated with an Atomic Pt Layer for the Oxygen Reduction Reaction

DOE PAGES

Tian, Xinlong; Tang, Haibo; Luo, Junming; ...

2017-04-25

A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less