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.

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.

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

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.

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.

Water geochemistry of shallow lakes from the southeastern Pampa plain, Argentina and their implications on mollusk shells preservation.

PubMed

Cristini, Paula A; Tietze, Eleonor; De Francesco, Claudio G; Martínez, Daniel E

2017-12-15

A seasonal sampling of sediments, column and interstitial water for physico-chemical analysis were performed in littoral and open water areas in three freshwater shallow lakes (Nahuel Rucá, Las Mostazas and Los Carpinchos) from Southeastern Pampa plain, Argentina. The main objective of the present study is to evaluate how the characteristics of the depositional environments could be affecting mollusk shell preservation. These lakes are very shallow (2m) and are characterized by an extensive littoral area, dominated by the emergent macrophyte Schoenoplectus californicus, which forms a complete ring around the lake, and an open water area, in general free of vegetation. Five samples of sediments in each compartment were extracted for analysis of pH, moisture, organic matter and carbonates content using a gravity corer, while five samples from column and interstitial water were extracted for chemical analysis (pH, conductivity, major ions, minor ions and hardness). Besides, calcite and aragonite saturation indices and the redox potential were calculated for each lake. The results show the significant impact of water chemistry and redox conditions on the preservation potential of freshwater mollusk and consequently in the quality of paleonvironmental reconstruction based on the biological record from the study region. The higher concentration of organic matter and lower pH registered in the littoral area, mainly during warm months (autumn and summer), suggest worst environments for mollusk preservation, compared to open waters. Moreover, water geochemistry analysis showed aragonite and calcite indices near equilibrium or slightly subsaturated in interstitial water associated with more acid pHs, while column water is strongly oversaturated related to alkaline pHs. These results suggest that carbonate remains within sediments will be subject to dissolution affecting negatively their preservation potential. However, mollusk shells in contact with the column water are not expected to be dissolved. Copyright © 2017 Elsevier B.V. All rights reserved.

Core/multishell nanowire heterostructures as multicolor, high-efficiency light-emitting diodes.

PubMed

Qian, Fang; Gradecak, Silvija; Li, Yat; Wen, Cheng-Yen; Lieber, Charles M

2005-11-01

We report the growth and characterization of core/multishell nanowire radial heterostructures, and their implementation as efficient and synthetically tunable multicolor nanophotonic sources. Core/multishell nanowires were prepared by metal-organic chemical vapor deposition with an n-GaN core and InxGa1-xN/GaN/p-AlGaN/p-GaN shells, where variation of indium mole fraction is used to tune emission wavelength. Cross-sectional transmission electron microscopy studies reveal that the core/multishell nanowires are dislocation-free single crystals with a triangular morphology. Energy-dispersive X-ray spectroscopy clearly shows shells with distinct chemical compositions, and quantitatively confirms that the thickness and composition of individual shells can be well controlled during synthesis. Electrical measurements show that the p-AlGaN/p-GaN shell structure yields reproducible hole conduction, and electroluminescence measurements demonstrate that in forward bias the core/multishell nanowires function as light-emitting diodes, with tunable emission from 365 to 600 nm and high quantum efficiencies. The ability to synthesize rationally III-nitride core/multishell nanowire heterostructures opens up significant potential for integrated nanoscale photonic systems, including multicolor lasers.

Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

NASA Astrophysics Data System (ADS)

Liu, Y.-W.; Aciego, S. M.; Wanamaker, A. D., Jr.

2015-02-01

Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore it is important to investigate how environmental factors (seawater pH, temperature and salinity) influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (87Sr / 86Sr and δ88 / 86Sr) and boron (δ11B) isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica). The 87Sr / 86Sr ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The 84Sr-87Sr double spike resolved shell δ 88 / 86Sr and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 °C. The δ11B records from the experiment show at least a 5‰ increase through the culture season (January 2010-August 2010), with low values from beginning to week 19 and higher values hereafter. The larger range in δ11B in this experiment compared to predictions based on other carbonate organisms (2-3‰) suggests that a species-specific fractionation factor may be required. A relatively strong correlation between the Δ pH (pHshell-pHsw) and seawater pH (pHsw) was observed (R2 = 0.34), which suggests that A. islandica partly regulates the pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 34% of the variance in the δ11B data. Instead, a rapid rise in δ11B after week 19 suggests that the boron uptake of the shell changes when a temperature threshold of 13 °C is reached.

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.

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.

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

Theory and practice of uncommon molecular electronic configurations.

PubMed

Gryn'ova, Ganna; Coote, Michelle L; Corminboeuf, Clemence

2015-01-01

The electronic configuration of the molecule is the foundation of its structure and reactivity. The spin state is one of the key characteristics arising from the ordering of electrons within the molecule's set of orbitals. Organic molecules that have open-shell ground states and interesting physicochemical properties, particularly those influencing their spin alignment, are of immense interest within the up-and-coming field of molecular electronics. In this advanced review, we scrutinize various qualitative rules of orbital occupation and spin alignment, viz., the aufbau principle, Hund's multiplicity rule, and dynamic spin polarization concept, through the prism of quantum mechanics. While such rules hold in selected simple cases, in general the spin state of a system depends on a combination of electronic factors that include Coulomb and Pauli repulsion, nuclear attraction, kinetic energy, orbital relaxation, and static correlation. A number of fascinating chemical systems with spin states that fluctuate between triplet and open-shell singlet, and are responsive to irradiation, pH, and other external stimuli, are highlighted. In addition, we outline a range of organic molecules with intriguing non-aufbau orbital configurations. In such quasi-closed-shell systems, the singly occupied molecular orbital (SOMO) is energetically lower than one or more doubly occupied orbitals. As a result, the SOMO is not affected by electron attachment to or removal from the molecule, and the products of such redox processes are polyradicals. These peculiar species possess attractive conductive and magnetic properties, and a number of them that have already been developed into molecular electronics applications are highlighted in this review. WIREs Comput Mol Sci 2015, 5:440-459. doi: 10.1002/wcms.1233 For further resources related to this article, please visit the WIREs website.

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.

Equation-of-motion coupled-cluster method for ionised states with spin-orbit coupling using open-shell reference wavefunction

NASA Astrophysics Data System (ADS)

Wang, Zhifan; Wang, Fan

2018-04-01

The equation-of-motion coupled-cluster method for ionised states at the singles and doubles level (EOM-IP-CCSD) with spin-orbit coupling (SOC) included in post-Hartree-Fock (HF) steps is extended to spatially non-degenerate open-shell systems such as high spin states of s1, p3, σ1 or π2 configuration in this work. Pseudopotentials are employed to treat relativistic effects and spin-unrestricted scalar relativistic HF determinant is adopted as reference in calculations. Symmetry is not exploited in the implementation since both time-reversal and spatial symmetry is broken due to SOC. IPs with the EOM-IP-CCSD approach are those from the 3Σ1- states for high spin state of π2 configuration, while the ground state is the 3Σ0- state. When removing an electron from the high spin state of p3 configuration, only the 3P2 state can be reached. The open-shell EOM-IP-CCSD approach with SOC was employed in calculating IPs of some open-shell atoms with s1 configuration, diatomic molecules with π2 configuration and SOC splitting of the ionised π1 state, as well as IPs of VA atoms with p3 configuration. Our results demonstrate that this approach can be applied to ionised states of spatially non-degenerate open-shell states containing heavy elements with reasonable accuracy.

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

Scalable Synthesis of Triple-Core-Shell Nanostructures of TiO2 @MnO2 @C for High Performance Supercapacitors Using Structure-Guided Combustion Waves.

PubMed

Shin, Dongjoon; Shin, Jungho; Yeo, Taehan; Hwang, Hayoung; Park, Seonghyun; Choi, Wonjoon

2018-03-01

Core-shell nanostructures of metal oxides and carbon-based materials have emerged as outstanding electrode materials for supercapacitors and batteries. However, their synthesis requires complex procedures that incur high costs and long processing times. Herein, a new route is proposed for synthesizing triple-core-shell nanoparticles of TiO 2 @MnO 2 @C using structure-guided combustion waves (SGCWs), which originate from incomplete combustion inside chemical-fuel-wrapped nanostructures, and their application in supercapacitor electrodes. SGCWs transform TiO 2 to TiO 2 @C and TiO 2 @MnO 2 to TiO 2 @MnO 2 @C via the incompletely combusted carbonaceous fuels under an open-air atmosphere, in seconds. The synthesized carbon layers act as templates for MnO 2 shells in TiO 2 @C and organic shells of TiO 2 @MnO 2 @C. The TiO 2 @MnO 2 @C-based electrodes exhibit a greater specific capacitance (488 F g -1 at 5 mV s -1 ) and capacitance retention (97.4% after 10 000 cycles at 1.0 V s -1 ), while the absence of MnO 2 and carbon shells reveals a severe degradation in the specific capacitance and capacitance retention. Because the core-TiO 2 nanoparticles and carbon shell prevent the deformation of the inner and outer sides of the MnO 2 shell, the nanostructures of the TiO 2 @MnO 2 @C are preserved despite the long-term cycling, giving the superior performance. This SGCW-driven fabrication enables the scalable synthesis of multiple-core-shell structures applicable to diverse electrochemical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

NASA Astrophysics Data System (ADS)

Liu, Y.-W.; Aciego, S. M.; Wanamaker, A. D., Jr.

2015-06-01

Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore, it is important to investigate how environmental factors (seawater pH, temperature and salinity) influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (87Sr / 86Sr and δ88 / 86Sr) and boron (δ11B) isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica). The 87Sr / 86Sr ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The 84Sr-87Sr double-spike-resolved shell δ88 / 86Sr and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 °C. The δ11B records from the experiment show at least a 5‰ increase through the 29-week culture season (January 2010-August 2010), with low values from the beginning to week 19 and higher values thereafter. The larger range in δ11B in this experiment compared to predictions based on other carbonate organisms (2-3‰) suggests that a species-specific fractionation factor may be required. A significant correlation between the ΔpH (pHshell - pHsw) and seawater pH (pHsw) was observed (R2 = 0.35), where the pHshell is the calcification pH of the shell calculated from boron isotopic composition. This negative correlation suggests that A. islandica partly regulates the pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 35% of the variance in the δ11B data. Instead, a rapid rise in δ11B of the shell material after week 19, during the summer, suggests that the boron uptake changes when a thermal threshold of > 13 °C is reached.

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.

Identification and characterization of a matrix protein (PPP-10) in the periostracum of the pearl oyster, Pinctada fucata.

PubMed

Nakayama, Seiji; Suzuki, Michio; Endo, Hirotoshi; Iimura, Kurin; Kinoshita, Shigeharu; Watabe, Shugo; Kogure, Toshihiro; Nagasawa, Hiromichi

2013-01-01

The periostracum is a layered structure that is formed as a mollusk shell grows. The shell is covered by the periostracum, which consists of organic matrices that prevent decalcification of the shell. In the present study, we discovered the presence of chitin in the periostracum and identified a novel matrix protein, Pinctada fucata periostracum protein named PPP-10. It was purified from the sodium dodecyl sulfate/dithiothreitol-soluble fraction of the periostracum of the Japanese pearl oyster, P. fucata. The deduced amino acid sequence was determined by a combination of amino acid sequence analysis and cDNA cloning. The open reading frame encoded a precursor protein of 112 amino acid residues including a 21-residue signal peptide. The 91 residues following the signal peptide contained abundant Cys and Tyr residues. PPP-10 was expressed on the outer side of the outer fold in the mantle, indicating that PPP-10 was present in the second or third layer of the periostracum. We also determined that the recombinant PPP-10 had chitin-binding activity and could incorporate chitin into the scaffolds of the periostracum. These results shed light on the early steps in mollusk shell formation.

Identification and characterization of a matrix protein (PPP-10) in the periostracum of the pearl oyster, Pinctada fucata☆

PubMed Central

Nakayama, Seiji; Suzuki, Michio; Endo, Hirotoshi; Iimura, Kurin; Kinoshita, Shigeharu; Watabe, Shugo; Kogure, Toshihiro; Nagasawa, Hiromichi

2013-01-01

The periostracum is a layered structure that is formed as a mollusk shell grows. The shell is covered by the periostracum, which consists of organic matrices that prevent decalcification of the shell. In the present study, we discovered the presence of chitin in the periostracum and identified a novel matrix protein, Pinctada fucata periostracum protein named PPP-10. It was purified from the sodium dodecyl sulfate/dithiothreitol-soluble fraction of the periostracum of the Japanese pearl oyster, P. fucata. The deduced amino acid sequence was determined by a combination of amino acid sequence analysis and cDNA cloning. The open reading frame encoded a precursor protein of 112 amino acid residues including a 21-residue signal peptide. The 91 residues following the signal peptide contained abundant Cys and Tyr residues. PPP-10 was expressed on the outer side of the outer fold in the mantle, indicating that PPP-10 was present in the second or third layer of the periostracum. We also determined that the recombinant PPP-10 had chitin-binding activity and could incorporate chitin into the scaffolds of the periostracum. These results shed light on the early steps in mollusk shell formation. PMID:24251105

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+.

The isotopic biosignatures of photo- vs. thiotrophic bivalves: are they preserved in fossil shells?

PubMed

Dreier, A; Loh, W; Blumenberg, M; Thiel, V; Hause-Reitner, D; Hoppert, M

2014-09-01

Symbiont-bearing and non-symbiotic marine bivalves were used as model organisms to establish biosignatures for the detection of distinctive symbioses in ancient bivalves. For this purpose, the isotopic composition of lipids (δ13C) and bulk organic shell matrix (δ13C, δ34S, δ15N) from shells of several thiotrophic, phototrophic, or non-symbiotic bivalves were compared (phototrophic: Fragum fragum, Fragum unedo, Tridacna maxima; thiotrophic: Codakia tigerina, Fimbria fimbriata, Anodontia sp.; non-symbiotic: Tapes dorsatus, Vasticardium vertebratum, Scutarcopagia sp.). ∆13C values of bulk organic shell matrices, most likely representing mainly original shell protein/chitin biomass, were depleted in thio- and phototrophic bivalves compared to non-symbiotic bivalves. As the bulk organic shell matrix also showed a major depletion of δ15N (down to -2.2 ‰) for thiotrophic bivalves, combined δ13C and δ15N values are useful to differentiate between thio-, phototrophic, and non-symbiotic lifestyles. However, the use of these isotopic signatures for the study of ancient bivalves is limited by the preservation of the bulk organic shell matrix in fossils. Substantial alteration was clearly shown by detailed microscopic analyses of fossil (late Pleistocene) T. maxima and Trachycardium lacunosum shell, demonstrating a severe loss of quantity and quality of bulk organic shell matrix with time. Likewise, the composition and δ13C-values of lipids from empty shells indicated that a large part of these compounds derived from prokaryotic decomposers. The use of lipids from ancient shells for the reconstruction of the bivalve's life style therefore appears to be restricted. © 2014 John Wiley & Sons Ltd.

Tuning the Thermoelectric Properties of a Conducting Polymer through Blending with Open-Shell Molecular Dopants.

PubMed

Tomlinson, Edward P; Willmore, Matthew J; Zhu, Xiaoqin; Hilsmier, Stuart W A; Boudouris, Bryan W

2015-08-26

Polymer thermoelectric devices are emerging as promising platforms by which to convert thermal gradients into electricity directly, and poly(3,4-ethylene dioxythiophene) doped with poly(styrenesulfonate) ( PSS) is a leading candidate in a number of these thermoelectric modules. Here, we implement the stable radical-bearing small molecule 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO-OH) as an intermolecular dopant in order to tune the electrical conductivity, thermopower, and power factor of PSS thin films. Specifically, we demonstrate that, at moderate loadings (∼2%, by weight) of the open-shell TEMPO-OH molecule, the thermopower of PSS thin films is increased without a marked decline in the electrical conductivity of the material. This effect, in turn, allows for an optimization of the power factor in the composite organic materials, which is a factor of 2 greater than the pristine PSS thin films. Furthermore, because the loading of TEMPO-OH is relatively low, we observe that there is little change in either the crystalline nature or surface topography of the composite films relative to the pristine PSS films. Instead, we determine that the increase in the thermopower is due to the presence of stable radical sites within the PSS that persist despite the highly acidic environment that occurs due to the presence of the poly(styrenesulfonate) moiety. Additionally, the oxidation-reduction-active (redox-active) nature of the TEMPO-OH small molecules provides a means by which to filter charges of different energy values. Therefore, these results demonstrate that a synergistic combination of an open-shell species and a conjugated polymer allows for enhanced thermoelectric properties in macromolecular systems, and as such, it offers the promise of a new design pathway in polymer thermoelectric materials.

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.

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.

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.

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.

Efficacy of antimicrobials extracted from organic pecan shell for inhibiting the growth of Listeria spp.

PubMed

Babu, Dinesh; Crandall, Philip G; Johnson, Casey L; O'Bryan, Corliss A; Ricke, Steven C

2013-12-01

Growers and processors of USDA certified organic foods are in need of suitable organic antimicrobials. The purpose of the research reported here was to develop and test natural antimicrobials derived from an all-natural by-product, organic pecan shells. Unroasted and roasted organic pecan shells were subjected to solvent free extraction to produce antimicrobials that were tested against Listeria spp. and L. monocytogenes serotypes to determine the minimum inhibitory concentrations (MIC) of antimicrobials. The effectiveness of pecan shell extracts were further tested using a poultry skin model system and the growth inhibition of the Listeria cells adhered onto the skin model were quantified. The solvent free extracts of pecan shells inhibited Listeria strains at MICs as low as 0.38%. The antimicrobial effectiveness tests on a poultry skin model exhibited nearly a 2 log reduction of the inoculated cocktail mix of Listeria strains when extracts of pecan shell powder were used. The extracts also produced greater than a 4 log reduction of the indigenous spoilage bacteria on the chicken skin. Thus, the pecan shell extracts may prove to be very effective alternative antimicrobials against food pathogens and supplement the demand for effective natural antimicrobials for use in organic meat processing. © 2013 Institute of Food Technologists®

Biodegradable Core-shell Dual-Metal-Organic-Frameworks Nanotheranostic Agent for Multiple Imaging Guided Combination Cancer Therapy

PubMed Central

Wang, Dongdong; Zhou, Jiajia; Shi, Ruohong; Wu, Huihui; Chen, Ruhui; Duan, Beichen; Xia, Guoliang; Xu, Pengping; Wang, Hui; Zhou, Shu; Wang, Chengming; Wang, Haibao; Guo, Zhen; Chen, Qianwang

2017-01-01

Metal-organic-frameworks (MOFs) possess high porosity, large surface area, and tunable functionality are promising candidates for synchronous diagnosis and therapy in cancer treatment. Although large number of MOFs has been discovered, conventional MOF-based nanoplatforms are mainly limited to the sole MOF source with sole functionality. In this study, surfactant modified Prussian blue (PB) core coated by compact ZIF-8 shell (core-shell dual-MOFs, CSD-MOFs) has been reported through a versatile stepwise approach. With Prussian blue as core, CSD-MOFs are able to serve as both magnetic resonance imaging (MRI) and fluorescence optical imaging (FOI) agents. We show that CSD-MOFs crystals loading the anticancer drug doxorubicin (DOX) are efficient pH and near-infrared (NIR) dual-stimuli responsive drug delivery vehicles. After the degradation of ZIF-8, simultaneous NIR irradiation to the inner PB MOFs continuously generate heat that kill cancer cells. Their efficacy on HeLa cancer cell lines is higher compared with the respective single treatment modality, achieving synergistic chemo-thermal therapy efficacy. In vivo results indicate that the anti-tumor efficacy of CSD-MOFs@DOX+NIR was 7.16 and 5.07 times enhanced compared to single chemo-therapy and single thermal-therapy respectively. Our strategy opens new possibilities to construct multifunctional theranostic systems through integration of two different MOFs. PMID:29158848

Ambient Stable Radical Cations, Diradicaloid π-Dimeric Dications, Closed-Shell Dications, and Diradical Dications of Methylthio-Capped Rylenes.

PubMed

Qi, Qingbiao; Burrezo, Paula Mayorga; Phan, Hoa; Herng, Tun Seng; Gopalakrishna, Tullimilli Y; Zeng, Wangdong; Ding, Jun; Casado, Juan; Wu, Jishan

2017-06-01

Radical cations and dications of π-conjugated systems play vital roles in organic electronic devices, organic conductors, and conducting polymers. Their structures, charge and spin distribution, and mechanism of charge transport are of great interest. In this article, radical cations and dications of a series of newly synthesized methylthio-capped rylenes were synthesized and isolated. Their ground-state structures, physical properties, and solid-state packing were systematically investigated by various experimental methods, such as X-ray crystallographic analysis, UV/Vis/NIR absorption spectroscopy, (spectro-)electrochemistry, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, superconducting quantum interference device, and Raman spectroscopy, assisted by DFT calculations. It was found that all the charged species show an exceptional stability under ambient air and light conditions due to the efficient spin and charge delocalization over the whole rylene backbone. The dication of hexarylene turned out to have an unusual open-shell singlet rather than closed-shell ground state, thus it can be described as a diradical dication. Dimerization was observed for the radical cations and even the dications in crystals due to the strong intermolecular antiferromagnetic spin-spin interaction and π-π interaction, which result in unique magnetic properties. Such intermolecular association was also observed in solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Soil calcium availability influences shell ecophenotype formation in the sub-antarctic land snail, Notodiscus hookeri.

PubMed

Charrier, Maryvonne; Marie, Arul; Guillaume, Damien; Bédouet, Laurent; Le Lannic, Joseph; Roiland, Claire; Berland, Sophie; Pierre, Jean-Sébastien; Le Floch, Marie; Frenot, Yves; Lebouvier, Marc

2013-01-01

Ecophenotypes reflect local matches between organisms and their environment, and show plasticity across generations in response to current living conditions. Plastic responses in shell morphology and shell growth have been widely studied in gastropods and are often related to environmental calcium availability, which influences shell biomineralisation. To date, all of these studies have overlooked micro-scale structure of the shell, in addition to how it is related to species responses in the context of environmental pressure. This study is the first to demonstrate that environmental factors induce a bi-modal variation in the shell micro-scale structure of a land gastropod. Notodiscus hookeri is the only native land snail present in the Crozet Archipelago (sub-Antarctic region). The adults have evolved into two ecophenotypes, which are referred to here as MS (mineral shell) and OS (organic shell). The MS-ecophenotype is characterised by a thick mineralised shell. It is primarily distributed along the coastline, and could be associated to the presence of exchangeable calcium in the clay minerals of the soils. The Os-ecophenotype is characterised by a thin organic shell. It is primarily distributed at high altitudes in the mesic and xeric fell-fields in soils with large particles that lack clay and exchangeable calcium. Snails of the Os-ecophenotype are characterised by thinner and larger shell sizes compared to snails of the MS-ecophenotype, indicating a trade-off between mineral thickness and shell size. This pattern increased along a temporal scale; whereby, older adult snails were more clearly separated into two clusters compared to the younger adult snails. The prevalence of glycine-rich proteins in the organic shell layer of N. hookeri, along with the absence of chitin, differs to the organic scaffolds of molluscan biominerals. The present study provides new insights for testing the adaptive value of phenotypic plasticity in response to spatial and temporal environmental variations.

Soil Calcium Availability Influences Shell Ecophenotype Formation in the Sub-Antarctic Land Snail, Notodiscus hookeri

PubMed Central

Charrier, Maryvonne; Marie, Arul; Guillaume, Damien; Bédouet, Laurent; Le Lannic, Joseph; Roiland, Claire; Berland, Sophie; Pierre, Jean-Sébastien; Le Floch, Marie; Frenot, Yves; Lebouvier, Marc

2013-01-01

Ecophenotypes reflect local matches between organisms and their environment, and show plasticity across generations in response to current living conditions. Plastic responses in shell morphology and shell growth have been widely studied in gastropods and are often related to environmental calcium availability, which influences shell biomineralisation. To date, all of these studies have overlooked micro-scale structure of the shell, in addition to how it is related to species responses in the context of environmental pressure. This study is the first to demonstrate that environmental factors induce a bi-modal variation in the shell micro-scale structure of a land gastropod. Notodiscus hookeri is the only native land snail present in the Crozet Archipelago (sub-Antarctic region). The adults have evolved into two ecophenotypes, which are referred to here as MS (mineral shell) and OS (organic shell). The MS-ecophenotype is characterised by a thick mineralised shell. It is primarily distributed along the coastline, and could be associated to the presence of exchangeable calcium in the clay minerals of the soils. The Os-ecophenotype is characterised by a thin organic shell. It is primarily distributed at high altitudes in the mesic and xeric fell-fields in soils with large particles that lack clay and exchangeable calcium. Snails of the Os-ecophenotype are characterised by thinner and larger shell sizes compared to snails of the MS- ecophenotype, indicating a trade-off between mineral thickness and shell size. This pattern increased along a temporal scale; whereby, older adult snails were more clearly separated into two clusters compared to the younger adult snails. The prevalence of glycine-rich proteins in the organic shell layer of N. hookeri, along with the absence of chitin, differs to the organic scaffolds of molluscan biominerals. The present study provides new insights for testing the adaptive value of phenotypic plasticity in response to spatial and temporal environmental variations. PMID:24376821

Data on Molluscan Shells in parts of Nellore Coast, southeast coast of India.

PubMed

Lakshmanna, B; Jayaraju, N; Prasad, T Lakshmi; Sreenivasulu, G; Nagalakshmi, K; Kumar, M Pramod; Madakka, M

2018-02-01

X-ray diffraction (XRD), Scanning Electron Microscope-Energy Dispersive Spectroscopy (SEM-EDS), and Fourier Transform Infrared Spectroscopy (FT-IR), were applied to analyze the organic matrix of two Molluscan shells . The Mollusca shells are mineral structure and calcium carbonate crystallized as aragonite. The FT-IR spectra showed Alkyl Halide, Alkanes, Alcohols, Amides, Aromatic, and Hydroxyl groups in the organic matrix of the whole (organic and mineral) Molluscan shells. SEM images of particles of the two Molluscan shells at different magnifications were taken. The morphologies of the samples show a flake like structures with irregular grains, their sizes are at micrometric scale and the chemical analysis of EDS indicated that the major elements of Cardita and Gastropoda were C, O, and Ca, consistent with the results of XRD analysis. The results of the analysis of the EDS spectra of the shells showed that the content of most of the powder composition of shells is the element carbon, calcium oxygen, aluminium, and lead peaks that appear on the Cardita and Gastropoda and shells powders tap EDS spectra. The present work examined organic matrix of the selected shells of the heavily polluted and light polluted sites, along Nellore Coast, South East Coast of India. The heavily polluted sites have significantly thickened shells. The data demonstrated the sensitivity of this abundant and widely distributed intertidal fragile environment.

Effects of hypoxia and non-lethal shell damage on shell mechanical and geochemical properties of a calcifying polychaete

NASA Astrophysics Data System (ADS)

Leung, Jonathan Y. S.; Cheung, Napo K. M.

2018-06-01

Calcification is a vital biomineralization process where calcifying organisms construct their calcareous shells for protection. While this process is expected to deteriorate under hypoxia, which reduces the metabolic energy yielded by aerobic respiration, some calcifying organisms were shown to maintain normal shell growth. The underlying mechanism remains largely unknown, but may be related to changing shell mineralogical properties, whereby shell growth is sustained at the expense of shell quality. Thus, we examined whether such plastic response is exhibited to alleviate the impact of hypoxia on calcification by assessing the shell growth and shell properties of a calcifying polychaete in two contexts (life-threatening and unthreatened conditions). Although hypoxia substantially reduced respiration rate (i.e., less metabolic energy produced), shell growth was only slightly hindered without weakening mechanical strength under unthreatened conditions. Unexpectedly, hypoxia did not undermine defence response (i.e., enhanced shell growth and mechanical strength) under life-threatening conditions, which may be attributed to the changes in mineralogical properties (e.g., increased calcite / aragonite) to reduce the energy demand for calcification. While more soluble shells (e.g., increased Mg / Ca in calcite) were produced under hypoxia as the trade-off, our findings suggest that mineralogical plasticity could be fundamental for calcifying organisms to maintain calcification under metabolic stress conditions.

Glass shell manufacturing in space. [residual gases in spherical shells made from metal-organic gels

NASA Technical Reports Server (NTRS)

Nolen, R. J.; Ebner, M. A.; Downs, R. L.

1980-01-01

Residual gases always found in glass shells are CO2, O2 and N2. In those cases where high water vapor pressure is maintained in the furnace, water is also found in the shells. Other evidence for the existence of water in shells is the presence of water-induced surface weathering of the interior shell surface. Water and CO2 are the predominant volatiles generated by the pyrolysis of both inorganic and hydrolyzed metal-organic gels. The pyrolysates of unhydrolyzed metal-organic gels also contain, in addition to water and CO2, significant levels of organic volatiles, such as ethanol and some hydrocarbons; on complete oxidation, these produce CO2 and water as well. Water is most likely the initial blowing agent, it is produced copiously during the initial stages of heating. In the later stages, CO2 becomes the dominant gas as H2O is lost at increasing rates. Water in the shell arises mainly from gel dehydration, CO2 by sodium bicarbonate/carbonate decomposition and carbon oxidation, and O2 and N2 by permeation of the ambient furnace air through the molten shell wall.

Organic Stable Isotopes in Ancient Oyster Shell Trace Pre-colonial Nitrogen Sources

NASA Astrophysics Data System (ADS)

Darrow, E. S.; Carmichael, R. H.; Andrus, C. F. T.; Jackson, H. E.

2016-02-01

Oysters (Crassostrea virginica) were an important food resource for native peoples of the northern Gulf of Mexico, who harvested oysters and deposited waste shell and other artifacts in middens. Shell δ15N is a proxy for oyster tissue δ15N that reflects nitrogen (N) in food sources of bivalves. We tested the use of shell δ15N as a paleo proxy of ancient N sources, which to our knowledge has not been previously done for archeological bivalve specimens. To determine δ15N of the very low-N and high-carbonate ancient specimens, we tested established and modified acidification techniques developed for modern clams and oysters to decalcify organic shell matrix and extract sufficient N for analyses. Centrifugation following acidification better concentrated N from ancient shells for stable isotope analysis. Careful screening was required to detect effects of diagenesis, incomplete acidification, and sample contamination. Modern oyster shells did not require acidification and bulk shell material was directly analyzed for δ15N using an EA-IRMS coupled to a CO2 trap. δ15N values in ancient oyster shells did not differ from modern oyster shells from the same sites, but %N and % organic carbon (C) were lower in ancient than in modern shells. Organic δ13C in ancient shells had a significant negative relationship with shell age, possibly due to an effect of sea level rise increasing marine suspended particulate matter (SPM) sources to oysters. In modern oysters, δ15N had a significant relationship with soft tissue δ15N, and predicted by SPM δ15N, water column nitrate, and water column dissolved organic nitrogen (DON) concentrations, demonstrating the effectiveness of oyster shell δ15N to identify N sources to bivalves such as oysters. Our study has demonstrated the usefulness of δ15N from midden oyster shells as a proxy for N sources in an estuary that has undergone relatively light impacts from human land-use change through the past 2000 years.

Efficient and accurate local single reference correlation methods for high-spin open-shell molecules using pair natural orbitals

NASA Astrophysics Data System (ADS)

Hansen, Andreas; Liakos, Dimitrios G.; Neese, Frank

2011-12-01

A production level implementation of the high-spin open-shell (spin unrestricted) single reference coupled pair, quadratic configuration interaction and coupled cluster methods with up to doubly excited determinants in the framework of the local pair natural orbital (LPNO) concept is reported. This work is an extension of the closed-shell LPNO methods developed earlier [F. Neese, F. Wennmohs, and A. Hansen, J. Chem. Phys. 130, 114108 (2009), 10.1063/1.3086717; F. Neese, A. Hansen, and D. G. Liakos, J. Chem. Phys. 131, 064103 (2009), 10.1063/1.3173827]. The internal space is spanned by localized orbitals, while the external space for each electron pair is represented by a truncated PNO expansion. The laborious integral transformation associated with the large number of PNOs becomes feasible through the extensive use of density fitting (resolution of the identity (RI)) techniques. Technical complications arising for the open-shell case and the use of quasi-restricted orbitals for the construction of the reference determinant are discussed in detail. As in the closed-shell case, only three cutoff parameters control the average number of PNOs per electron pair, the size of the significant pair list, and the number of contributing auxiliary basis functions per PNO. The chosen threshold default values ensure robustness and the results of the parent canonical methods are reproduced to high accuracy. Comprehensive numerical tests on absolute and relative energies as well as timings consistently show that the outstanding performance of the LPNO methods carries over to the open-shell case with minor modifications. Finally, hyperfine couplings calculated with the variational LPNO-CEPA/1 method, for which a well-defined expectation value type density exists, indicate the great potential of the LPNO approach for the efficient calculation of molecular properties.

Research advances in polymer emulsion based on "core-shell" structure particle design.

PubMed

Ma, Jian-zhong; Liu, Yi-hong; Bao, Yan; Liu, Jun-li; Zhang, Jing

2013-09-01

In recent years, quite many studies on polymer emulsions with unique core-shell structure have emerged at the frontier between material chemistry and many other fields because of their singular morphology, properties and wide range of potential applications. Organic substance as a coating material onto either inorganic or organic internal core materials promises an unparalleled opportunity for enhancement of final functions through rational designs. This contribution provides a brief overview of recent progress in the synthesis, characterization, and applications of both inorganic-organic and organic-organic polymer emulsions with core-shell structure. In addition, future research trends in polymer composites with core-shell structure are also discussed in this review. Copyright © 2013 Elsevier B.V. All rights reserved.

Comment on Peck et al: Vulnerability of pteropod (Limacina helicina) to ocean acidification: shell dissolution occurs despite an intact organic layer

NASA Astrophysics Data System (ADS)

Bednaršek, N.; Johnson, J.; Feely, R. A.

2016-05-01

Pteropods have been recognized as one of the most sensitive marine organisms to ocean acidification (OA). Their susceptibility is mostly related to rapid shell dissolution, which is correlated with exposure to waters undersaturated with respect to aragonite (Ωar≤ 1) (e.g., Lischka et al., 2011; Bednaršek et al., 2012a,b, 2014a,b; Busch et al., 2014). Increased dissolution weakens the shell, increases vulnerability to predation and infection, and imposes an energetic cost. The rapidity of shell dissolution is attributed to the combination of metastable aragonitic crystal structure of shells that are among the thinnest known for calcifying organisms, and an extremely thin outer organic layer (i.e. periostracum <1 μm thick), suggesting insufficient protection against shell dissolution at Ωar≤1 (Bednaršek et al., 2014b). The periostracum generally consists of polysaccharide and proteinaceous components (Gaffey and Bronnimann, 1993) but varies significantly in its structure and composition amongst taxa.

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.

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)

Ocean acidification alters the material properties of Mytilus edulis shells

PubMed Central

Fitzer, Susan C.; Zhu, Wenzhong; Tanner, K. Elizabeth; Phoenix, Vernon R.; Kamenos, Nicholas A.; Cusack, Maggie

2015-01-01

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis, was cultured at projected levels of pCO2 (380, 550, 750, 1000 µatm) and increased temperatures (ambient, ambient plus 2°C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus (E), hardness (H) and toughness (KIC) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean pCO2 and temperatures as projected for future global ocean appears to reduce the impact of increasing pCO2 on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature. PMID:25540244

Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

USGS Publications Warehouse

Takesue, R.K.; Bacon, C.R.; Thompson, J.K.

2008-01-01

A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carr?? et al. [Carr?? M., Bentaleb I., Bruguier O., Ordinola E., Barrett N. T. and Fontugne M. (2006) Calcification rate influence on trace element concentrations in aragonitic bivalve shells: evidences and mechanisms. Geochim. Cosmochim. Acta 70, 4906-4920] which predicts that [M]/Ca ratios increase as calcification rates increase and Ca2+ channel specificity decreases. This result, in combination with the possibility that there were ontogenetic variations in growth rates among individuals younger than 2 years, underscores the need to develop an independent age model for C. amurensis shells. If growth-rate effects on lattice-bound [M]/Ca ratios can be constrained, it may yet be possible to develop high-resolution geochemical proxies for external solution chemistry in low-salinity regions of SFB.

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.

Biocolloids with ordered urease multilayer shells as enzymatic reactors.

PubMed

Lvov, Y; Caruso, F

2001-09-01

The preparation of biocolloids with organized enzyme-containing multilayer shells for exploitation as colloidal enzymatic nanoreactors is described. Urease multilayers were assembled onto submicrometer-sized polystyrene spheres by the sequential adsorption of urease and polyelectrolyte, in a predetermined order, utilizing electrostatic interactions for layer growth. The catalytic activity of the biocolloids increased proportionally with the number of urease layers deposited on the particles, demonstrating that biocolloid particles with tailored enzymatic activities can be produced. It was further found that precoating the latex spheres with nanoparticles (40-nm silica or 12-nm magnetite) enhanced both the stability (with respect to adsorption) and enzymatic activity of the urease multilayers. The presence of the magnetite nanoparticle coating also provided a magnetic function that allowed the biocolloids to be easily and rapidly separated with a permanent magnet. The fabrication of such colloids opens new avenues for the application of bioparticles and represents a promising route for the creation of complex catalytic particles.

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...

Radionuclides, Trace Metals, and Organic Compounds in Shells of Native Freshwater Mussels Along the Hanford Reach of the Columbia River: 6000 Years Before Present to Current Times

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

B. L. Tiller; T. E. Marceau

2006-01-25

This report documents concentrations of radionuclides, trace metals, and semivolatile organic compounds measured in shell samples of the western pearl shell mussel collected along the Hanford Reach of the Columbia River.

Toughening mechanisms in laminated composites: A biomimetic study in mollusk shells

NASA Astrophysics Data System (ADS)

Kamat, Shekhar Shripad

2000-10-01

Mollusk shells can be described as structural biocomposite materials composed of a mineral (aragonite) and a continuous, albeit minor, organic (protein) component. The conch shell, Strombus Gigas, has intermediate strength and high fracture toughness. The high fracture toughness is a result of enhanced energy dissipation during crack propagation due to delamination, crack bridging, frictional sliding etc. A theoretical and experimental study was conducted on the crack bridging mechanisms operative in the shell. Four-point bend tests were conducted. Acoustic emission and post-mortem dye penetrants were used to characterize the crack propagation, together with conventional fractography. A two layer composite configuration is seen in the shells, with the tough and weak layers having a toughness ratio of ˜4 (Ktough = 2.2MPam1/2). This toughness ratio is a requisite for multiple cracking in the weak layer. A theoretical shear lag analysis of the crack bridging phenomena in the tough layer is shown to lead to a bridging law for the crack wake of the form of p = betau1/2 (p is the bridging traction for a crack opening u, with beta, being a constant of proportionality). Finite element analysis yielded a value of beta = 630 Nmm-5/2 and ucritical = 5 mum for the bridging law parameters. In a nonlinear fracture mechanics phenomenology, these values are relevant material parameters, rather than a critical stress intensity factor. The work of fracture for unnotched specimens is three orders of magnitude higher than mineral aragonite, and is demonstrated numerically incorporating the toughening mechanisms in the shell. Similar structural adaptations have been observed and studied in the red abalone shell, haliotis rufescens and the spines of the sea urchin, Heterocentrotus trigonarius. The toughening mechanisms seen in these shells give insight into structural design needs of brittle matrix composites (BMC) as well as conventional structural ceramics.

Pteropods counter mechanical damage and dissolution through extensive shell repair.

PubMed

Peck, Victoria L; Oakes, Rosie L; Harper, Elizabeth M; Manno, Clara; Tarling, Geraint A

2018-01-17

The dissolution of the delicate shells of sea butterflies, or pteropods, has epitomised discussions regarding ecosystem vulnerability to ocean acidification over the last decade. However, a recent demonstration that the organic coating of the shell, the periostracum, is effective in inhibiting dissolution suggests that pteropod shells may not be as susceptible to ocean acidification as previously thought. Here we use micro-CT technology to show how, despite losing the entire thickness of the original shell in localised areas, specimens of polar species Limacina helicina maintain shell integrity by thickening the inner shell wall. One specimen collected within Fram Strait with a history of mechanical and dissolution damage generated four times the thickness of the original shell in repair material. The ability of pteropods to repair and maintain their shells, despite progressive loss, demonstrates a further resilience of these organisms to ocean acidification but at a likely metabolic cost.

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.

rPM6 parameters for phosphorous and sulphur-containing open-shell molecules

NASA Astrophysics Data System (ADS)

Saito, Toru; Takano, Yu

2018-03-01

In this article, we have introduced a reparameterisation of PM6 (rPM6) for phosphorus and sulphur to achieve a better description of open-shell species containing the two elements. Two sets of the parameters have been optimised separately using our training sets. The performance of the spin-unrestricted rPM6 (UrPM6) method with the optimised parameters is evaluated against 14 radical species, which contain either phosphorus or sulphur atom, comparing with the original UPM6 and the spin-unrestricted density functional theory (UDFT) methods. The standard UPM6 calculations fail to describe the adiabatic singlet-triplet energy gaps correctly, and may cause significant structural mismatches with UDFT-optimised geometries. Leaving aside three difficult cases, tests on 11 open-shell molecules strongly indicate the superior performance of UrPM6, which provides much better agreement with the results of UDFT methods for geometric and electronic properties.

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.

Ocean acidification alters the material properties of Mytilus edulis shells.

PubMed

Fitzer, Susan C; Zhu, Wenzhong; Tanner, K Elizabeth; Phoenix, Vernon R; Kamenos, Nicholas A; Cusack, Maggie

2015-02-06

Ocean acidification (OA) and the resultant changing carbonate saturation states is threatening the formation of calcium carbonate shells and exoskeletons of marine organisms. The production of biominerals in such organisms relies on the availability of carbonate and the ability of the organism to biomineralize in changing environments. To understand how biomineralizers will respond to OA the common blue mussel, Mytilus edulis, was cultured at projected levels of pCO2 (380, 550, 750, 1000 µatm) and increased temperatures (ambient, ambient plus 2°C). Nanoindentation (a single mussel shell) and microhardness testing were used to assess the material properties of the shells. Young's modulus (E), hardness (H) and toughness (KIC) were measured in mussel shells grown in multiple stressor conditions. OA caused mussels to produce shell calcite that is stiffer (higher modulus of elasticity) and harder than shells grown in control conditions. The outer shell (calcite) is more brittle in OA conditions while the inner shell (aragonite) is softer and less stiff in shells grown under OA conditions. Combining increasing ocean pCO2 and temperatures as projected for future global ocean appears to reduce the impact of increasing pCO2 on the material properties of the mussel shell. OA may cause changes in shell material properties that could prove problematic under predation scenarios for the mussels; however, this may be partially mitigated by increasing temperature. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Mg-isotopic fractionation in the manila clam (Ruditapes philippinarum): New insights into Mg incorporation pathway and calcification process of bivalves

NASA Astrophysics Data System (ADS)

Planchon, Frédéric; Poulain, Céline; Langlet, Denis; Paulet, Yves-Marie; André, Luc

2013-11-01

We estimate the magnesium stable isotopic composition (δ26Mg) of the major compartments involved in the biomineralisation process of euryhaline bivalve, the manila clam Ruditapes philippinarum. Our aim is to identify the fractionation processes associated with Mg uptake and its cycling/transport in the bivalve organism, in order to better assess the controlling factors of the Mg isotopic records in bivalve shells. δ26Mg were determined in seawater, in hemolymph, extrapallial fluid (EPF), soft tissues and aragonitic shell of adult clams collected along the Auray River estuary (Gulf of Morbihan, France) at two sites showing contrasted salinity regimes. The large overall δ26Mg variations (4.16‰) demonstrate that significant mass-dependent Mg isotopic fractionations occur during Mg transfer from seawater to the aragonitic shell. Soft tissues span a range of fractionation factors relative to seawater (Δ26Mgsoft tissue-seawater) of 0.42 ± 0.12‰ to 0.76 ± 0.12‰, and show evidence for biological isotopic fractionation of Mg. Hemolymph and EPF are on average isotopically close to seawater (Δ26Mghemolymph-seawater = -0.20 ± 0.27‰; 2 sd; n = 5 and Δ26MgEPF-seawater = -0.23 ± 0.25‰; 2 sd; n = 5) indicating (1) a predominant seawater origin for Mg in the intercellular medium and (2) a relatively passive transfer route through the bivalve organism into the calcifying fluid. The lightest isotopic composition is found in shell, with δ26Mg ranging from -1.89 ± 0.07‰ to -4.22 ± 0.06‰. This range is the largest in the dataset and is proposed to result from a combination of abiotic and biologically-driven fractionation processes. Abiotic control includes fractionation during precipitation of aragonite and accounts for Δ26Mgaragonite-seawater ≈ 1000 ln αaragonite-seawater = -1.13 ± 0.28‰ at 20 °C based on literature data. Deviations from inorganic precipitate (expressed as Δ26MgPhysiol) appear particularly variable in the clam shell, ranging from 0.03‰ to -2.20‰, which indicates that bivalve shell formation can proceed either under fractionation similar to inorganically-precipitated aragonite or under variable physiological influences. These physiological isotopic effects may be consistent with a regulation of dissolved Mg content in hemolymph and/or EPF due to Mg incorporation into soft tissue and/or Mg fixation by organic macromolecules. Using closed- and open-system models we estimate that Δ26MgPhysiol can be satisfactorily resolved with a remaining Mg fraction in hemolymph and/or EPF of 74% down to 2%. However, this feature is not reflected in our hemolymph and EPF data and may indicate that regulation processes and isotopic fractionation may take place in self-contained spaces located close to calcification sites. The potential role of the shell organic matrix, which may host non-lattice-bound Mg in the shell, is also discussed but remains difficult to assess with our data. Regarding the large physiological effects, the δ26Mg record in the Manila clam shell offers limited potential as a proxy of temperature or seawater Mg isotopic composition. In contrast, the sensitivity of its δ26Mg to the salinity regime may offer an interesting tool to track changes in clam biological activity in estuarine environments.

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.

Comparison of Radiocarbon Ages of Sediments, Plants, and Shells From Coastal Lakes in North Florida

NASA Astrophysics Data System (ADS)

Wang, Y.; Das, O.; Liu, J.; Xu, X.; Roy, R.; Donoghue, J. F.; Means, G. H.

2017-12-01

Coastal lakes sediments are valuable archives of paleo-hurricanes and environmental changes during the late Quaternary provided that they can be accurately dated. Here, we report new radiocarbon (14C) dates derived from various organic and inorganic substrates, including bulk sediment organic matter, plants, shells, particulate organic matter (POM) and dissolved organic matter (DOM), from three coastal lakes in Florida, and compare these ages to evaluate the "reservoir effect" on 14C dating of both organic and inorganic carbon in these lakes. Bulk sediment organic matter yielded consistently older 14C ages than contemporaneous plants and shell fragments, indicating significant radiocarbon deficiencies in sedimentary organic matter in these coastal lakes, caused by influx of old organic carbon from terrestrial sources (such as soils and ancient peat deposits) in the watershed. Several reversals are observed in the 14C ages of bulk sediment organic matter in sediment cores from these lakes, indicating that input of aged organic matter from terrestrial sources into these lakes can vary considerably over time. DOM and POM samples collected at different times also yielded variable 14C signatures, further confirming the temporal variability in the contribution of old organic carbon from terrestrial sources to the lakes. The 14C age discrepancy between bulk sediment organic matter and co-occurring plant fragments or shells varies from less than one hundred years to nearly three thousand years in sediment cores examined in this study. The results show that 14C ages obtained from bulk sediment organic matter in these coastal lakes are unreliable. Analyses of both modern and fossil shells from one of the lakes suggest that the 14C reservoir effect on inorganic carbon in the lake is small and thus freshwater shells (if preserved in the sediment cores) may serve as a good substrate for 14C dating in the absence of plant fragments. However, unidentifiable shell fragments, especially those associated with sand pockets (or sand layers), in coastal lake sediment cores are not suitable for 14C dating as they are likely of marine origin and affected by significant marine 14C reservoir effect.

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.

Mineralogical Plasticity Acts as a Compensatory Mechanism to the Impacts of Ocean Acidification.

PubMed

Leung, Jonathan Y S; Russell, Bayden D; Connell, Sean D

2017-03-07

Calcifying organisms are considered particularly susceptible to the future impacts of ocean acidification (OA), but recent evidence suggests that they may be able to maintain calcification and overall fitness. The underlying mechanism remains unclear but may be attributed to mineralogical plasticity, which modifies the energetic cost of calcification. To test the hypothesis that mineralogical plasticity enables the maintenance of shell growth and functionality under OA conditions, we assessed the biological performance of a gastropod (respiration rate, feeding rate, somatic growth, and shell growth of Austrocochlea constricta) and analyzed its shell mechanical and geochemical properties (shell hardness, elastic modulus, amorphous calcium carbonate, calcite to aragonite ratio, and magnesium to calcium ratio). Despite minor metabolic depression and no increase in feeding rate, shell growth was faster under OA conditions, probably due to increased precipitation of calcite and trade-offs against inner shell density. In addition, the resulting shell was functionally suitable for increasingly "corrosive" oceans, i.e., harder and less soluble shells. We conclude that mineralogical plasticity may act as a compensatory mechanism to maintain overall performance of calcifying organisms under OA conditions and could be a cornerstone of calcifying organisms to acclimate to and maintain their ecological functions in acidifying oceans.

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

Pecan shell-based granular activated carbon for treatment of chemical oxygen demand (COD) in municipal wastewater.

PubMed

Bansode, R R; Losso, J N; Marshall, W E; Rao, R M; Portier, R J

2004-09-01

The present investigation was undertaken to compare the adsorption efficiency of pecan shell-based granular activated carbon with the adsorption efficiency of the commercial carbon Filtrasorb 200 with respect to uptake of the organic components responsible for the chemical oxygen demand (COD) of municipal wastewater. Adsorption efficiencies for these two sets of carbons (experimental and commercial) were analyzed by the Freundlich adsorption model. The results indicate that steam-activated and acid-activated pecan shell-based carbons had higher adsorption for organic matter measured as COD, than carbon dioxide-activated pecan shell-based carbon or Filtrasorb 200 at all the carbon dosages used during the experiment. The higher adsorption may be related to surface area as the two carbons with the highest surface area also had the highest organic matter adsorption. These results show that granular activated carbons made from agricultural waste (pecan shells) can be used with greater effectiveness for organic matter removal from municipal wastewater than a coal-based commercial carbon. Copyright 2004 Elsevier Ltd.

Adsorption of volatile organic compounds by pecan shell- and almond shell-based granular activated carbons.

PubMed

Bansode, R R; Losso, J N; Marshall, W E; Rao, R M; Portier, R J

2003-11-01

The objective of this research was to determine the effectiveness of using pecan and almond shell-based granular activated carbons (GACs) in the adsorption of volatile organic compounds (VOCs) of health concern and known toxic compounds (such as bromo-dichloromethane, benzene, carbon tetrachloride, 1,1,1-trichloromethane, chloroform, and 1,1-dichloromethane) compared to the adsorption efficiency of commercially used carbons (such as Filtrasorb 200, Calgon GRC-20, and Waterlinks 206C AW) in simulated test medium. The pecan shell-based GACs were activated using steam, carbon dioxide or phosphoric acid. An almond shell-based GAC was activated with phosphoric acid. Our results indicated that steam- or carbon dioxide-activated pecan shell carbons were superior in total VOC adsorption to phosphoric acid-activated pecan shell or almond shell carbons, inferring that the method of activation selected for the preparation of activated carbons affected the adsorption of VOCs and hence are factors to be considered in any adsorption process. The steam-activated, pecan shell carbon adsorbed more total VOCs than the other experimental carbons and had an adsorption profile similar to the two coconut shell-based commercial carbons, but had greater adsorption than the coal-based commercial carbon. All the carbons studied adsorbed benzene more effectively than the other organics. Pecan shell, steam-activated and acid-activated GACs showed higher adsorption of 1,1,1-trichloroethane than the other carbons studied. Multivariate analysis was conducted to group experimental carbons and commercial carbons based on their physical, chemical, and adsorptive properties. The results of the analysis conclude that steam-activated and acid-activated pecan shell carbons clustered together with coal-based and coconut shell-based commercial carbons, thus inferring that these experimental carbons could potentially be used as alternative sources for VOC adsorption in an aqueous environment.

Synthesis and characterization of triangulene

NASA Astrophysics Data System (ADS)

Pavliček, Niko; Mistry, Anish; Majzik, Zsolt; Moll, Nikolaj; Meyer, Gerhard; Fox, David J.; Gross, Leo

2017-05-01

Triangulene, the smallest triplet-ground-state polybenzenoid (also known as Clar's hydrocarbon), has been an enigmatic molecule ever since its existence was first hypothesized. Despite containing an even number of carbons (22, in six fused benzene rings), it is not possible to draw Kekulé-style resonant structures for the whole molecule: any attempt results in two unpaired valence electrons. Synthesis and characterization of unsubstituted triangulene has not been achieved because of its extreme reactivity, although the addition of substituents has allowed the stabilization and synthesis of the triangulene core and verification of the triplet ground state via electron paramagnetic resonance measurements. Here we show the on-surface generation of unsubstituted triangulene that consists of six fused benzene rings. The tip of a combined scanning tunnelling and atomic force microscope (STM/AFM) was used to dehydrogenate precursor molecules. STM measurements in combination with density functional theory (DFT) calculations confirmed that triangulene keeps its free-molecule properties on the surface, whereas AFM measurements resolved its planar, threefold symmetric molecular structure. The unique topology of such non-Kekulé hydrocarbons results in open-shell π-conjugated graphene fragments that give rise to high-spin ground states, potentially useful in organic spintronic devices. Our generation method renders manifold experiments possible to investigate triangulene and related open-shell fragments at the single-molecule level.

Bioconversion reactor

DOEpatents

McCarty, Perry L.; Bachmann, Andre

1992-01-01

A bioconversion reactor for the anaerobic fermentation of organic material. The bioconversion reactor comprises a shell enclosing a predetermined volume, an inlet port through which a liquid stream containing organic materials enters the shell, and an outlet port through which the stream exits the shell. A series of vertical and spaced-apart baffles are positioned within the shell to force the stream to flow under and over them as it passes from the inlet to the outlet port. The baffles present a barrier to the microorganisms within the shell causing them to rise and fall within the reactor but to move horizontally at a very slow rate. Treatment detention times of one day or less are possible.

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

Flexible 3D Fe@VO2 core-shell mesh: A highly efficient and easy-recycling catalyst for the removal of organic dyes.

PubMed

Li, Jing; Wang, Ruoqi; Su, Zhen; Zhang, Dandan; Li, Heping; Yan, Youwei

2018-10-01

Nowadays, it is extremely urgent to search for efficient and effective catalysts for water purification due to the severe worldwide water-contamination crises. Here, 3D Fe@VO 2 core-shell mesh, a highly efficient catalyst toward removal of organic dyes with excellent recycling ability in the dark is designed and developed for the first time. This novel core-shell structure is actually 304 stainless steel mesh coated by VO 2 , fabricated by an electrophoretic deposition method. In such a core-shell structure, Fe as the core allows much easier separation from the water, endowing the catalyst with a flexible property for easy recycling, while VO 2 as the shell is highly efficient in degradation of organic dyes with the addition of H 2 O 2 . More intriguingly, the 3D Fe@VO 2 core-shell mesh exhibits favorable performance across a wide pH range. The 3D Fe@VO 2 core-shell mesh can decompose organic dyes both in a light-free condition and under visible irradiation. The possible catalytic oxidation mechanism of Fe@VO 2 /H 2 O 2 system is also proposed in this work. Considering its facile fabrication, remarkable catalytic efficiency across a wide pH range, and easy recycling characteristic, the 3D Fe@VO 2 core-shell mesh is a newly developed high-performance catalyst for addressing the universal water crises. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Controlling factors of recent clastic coastal sediments (Viransehir, Mersin bay, S Turkey)

NASA Astrophysics Data System (ADS)

Gül, Murat; Özbek, Ahmet; Kurt, Mehmet Ali; Zorlu, Kemal

2009-04-01

The Plio-Quaternary conglomeratic sets within the marine environment of the Viranşehir coast (W Mersin, S Turkey) are responsible for the evolution of sandy and gravely beaches due to their control on various factors such as sea floor irregularity, wave energy, and organic activity. The conglomeratic sets close to the shoreline (50-150 cm) act as wave breakers, creating hard substratum and high energy, well-oxygenated environment for organisms like Patella sp., Phoronida worms and Brachidontes pharaonis (Fischer P. 1870). The boring activities of these organisms have disintegrated the sandy matrix of these sets. Finer-grained matrix sediments have been transported to the interset and open sea, while cobble-pebbles have been carried landwards and have created imbricated gravely beach deposits without matrix. Sandy beach is evolving where the conglomeratic sets away from the shoreline (5.0-10.0 m). In this example, sets form a bar; causing fivefold division as backshore, berm, surf zone, bar and offshore from land to sea. Poorly sorted, cobbles-pebbles cobbles and pebbles are found associated with the high-energy environments of bars, whilst well-sorted sands are observed in low energetic environments on shore. The sets and recent shell fragments are the main sources of coastal sediments in Viranşehir. However, the amount of shell fragments decrease towards the active river mouth. This is due to sediment and fresh water influx from the river causing deteriorated temperature, salinity and light penetration of the marine environment resulting in less organic diversity.

PREFACE: New nuclear structure phenomena in the vicinity of closed shells

NASA Astrophysics Data System (ADS)

Johnson, A.; Wyss, R.

1995-01-01

The proceedings of the international symposium on "New Nuclear Structure Phenomena in the Vicinity of Closed Shells - SELMA 94", held in Stockholm, Uppsala and on the Baltic Sea from Aug. 30 - Sep. 3 are collected in this volume. Since almost 40% of the session time was kept open for discussions, it is difficult to give full justice to the character of the meeting in a written report. However, since also many posters are presented in this volume, we hope that some of the flavour of this lively symposium will pass onto the reader. We have chosen to group related contributions in order to facilitate the reading. Several articles, though, may fit into several categories. With the event of large detector arrays there has been a tremendous development in the field of nuclear spectroscopy. The discovery of super-deformation has been followed by detailed spectroscopy in the second well. Hence, the concept of shell closure is reinterpreted in general terms, involving shapes different from spherical. Close to the drip lines, we expect new shells and new structure effects to emerge. Loosely bound neutrons may form a new state of nuclear matter. The regions of the nuclear chart far from the line of stability can be explored in the future by means of radioactive ion beams. New structure effects, that one might encounter far from the line of stability was one of the themes of this conference. The strong impact of the nuclear shell model is also evident in other branches of physics, like the structure of metal-clusters. Special attention was paid to the Sn-isotopes. In the Sn-isotopic chain, spectroscopic measurements are extending beyond the doubly-magic nucleus 132Sn. Large efforts have recently been made to study nuclei in the vicinity of the doubly-magic nucleus 100Sn, the other extreme end of the chain. Spectroscopic data on 100Sn would open the entire shell for nuclear structure studies, ranging over a number of 32 neutrons. During the organization of this meeting, the first 100Sn nuclei were observed at GSI, Germany, and in a subsequent experiment at GANIL, France. Results from these experiments were reported during the symposium as were much of the recent data around "classical" shell model nuclei. Neutron deficient nuclei in the Sn region show a variety of phenomena, such as coexisting shapes, enhanced quadrupole transitions etc. The role of intruder states in this mass region as well as the excitation pattern is still a puzzle for experimentalists and theoreticians and was discussed during the meeting. More work is needed until a unified picture of the structure of these nuclei will emerge. The combination of powerful mean-field models, large scale shell model calculations as well as new algebraic approaches to nuclear structure shows the strong and lively development in the field of nuclear theory as was evident from the presentations. It is obvious that great effort is needed to match the rapid development in the field of experimental nuclear structure. The organizing committee expresses special thanks to the Royal Swedish Academy of Sciences, through its Nobel Institute for Physics, for its generous support. We also want to thank the Royal Institute of Technology and Uppsala University for supporting this symposium. All this support was extremely essential for organizing the meeting as well as for rendering it success. We are very pleased about the possibility to print the proceedings of this meeting in Physics Scripta and thank their staff for helpful collaboration. Thanks also to the international advisory committee for its helpful work to select speakers and for suggestions. Conference secretary Inger Ericson's assistance during the meeting as well as the work of the organizing committee is highly appreciated. Finally, we like to thank all speakers and participants for making this symposium extremely lively and exciting. Last but not least: this symposium got its name from little Selma, born 19 January 1994, daughter of A Atac and J Nyberg.

Biometric studies on the bivalves Astarte elliptica, A. borealis and A. montagui in Kiel Bay (Western Baltic Sea)

NASA Astrophysics Data System (ADS)

Schaefer, R.; Trutschler, K.; Rumohr, H.

1985-09-01

The three Astarte species were studied in June 1983 at two sites in Kiel Bay, “Süderfahrt” and “Schleimünde”, at 20 m depth. Shell length to live wet weight correlations are given for all three species; for A. elliptica also shell-free dry weight, shell dry weight, ash-free dry weight of the soft body and ash-free dry weight of the shell are recorded as functions of the shell length. In the logarithmic length/weight regression analysis the coefficients of slope for A. elliptica and A. borealis are 3. For A. montagui, that coefficient is significantly greater than 3. Weight conversion factors, calculated for A. elliptica, revealed a mean weight composition of 31.5 % water in the mantle cavity and tissue water, 64.5 % shell ash, 2.1 % organic content of shell, 1.7 % organic content of the soft body and 0.4 % ash of the soft body. An isometric growth of shell length and shell breadth is confirmed for A. borealis, while A. montagui exhibits positive allometric shell growth and changes its shape during life.

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

Elevated CO2 affects shell dissolution rate but not calcification rate in a marine snail.

PubMed

Nienhuis, Sarah; Palmer, A Richard; Harley, Christopher D G

2010-08-22

As CO(2) levels increase in the atmosphere, so too do they in the sea. Although direct effects of moderately elevated CO(2) in sea water may be of little consequence, indirect effects may be profound. For example, lowered pH and calcium carbonate saturation states may influence both deposition and dissolution rates of mineralized skeletons in many marine organisms. The relative impact of elevated CO(2) on deposition and dissolution rates are not known for many large-bodied organisms. We therefore tested the effects of increased CO(2) levels--those forecast to occur in roughly 100 and 200 years--on both shell deposition rate and shell dissolution rate in a rocky intertidal snail, Nucella lamellosa. Shell weight gain per day in live snails decreased linearly with increasing CO(2) levels. However, this trend was paralleled by shell weight loss per day in empty shells, suggesting that these declines in shell weight gain observed in live snails were due to increased dissolution of existing shell material, rather than reduced production of new shell material. Ocean acidification may therefore have a greater effect on shell dissolution than on shell deposition, at least in temperate marine molluscs.

Field-assisted organization, substrate effects and magnetic behavior of Ag 30Co 70 core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Crisan, A. D.; Angelakeris, M.; Simeonidis, K.; Tsiaoussis, I.; Crisan, O.

2010-11-01

In core-shell systems with non-magnetic core and magnetic shell, the electron transport and magnetic properties are expected to show enhanced behavior due to the particular morpho-structural features of the conductive and magnetic regions. This may lead to novel advanced GMR materials and spin valves. This is the case of core-shell Ag-Co colloidal nanoscale particles that organize into regular arrays. An insight on the structure and morphology of the newly synthesized Ag-Co nanoparticles deposited on different substrates will be presented. The influence of the substrate on different morphologies and organization dynamics is discussed. It is shown that the magnetic behavior of the Ag-Co nanoparticles is highly influenced by the corona-like morphology of Co shell, chemical environment of the magnetic atoms and by the fact that they exhibit strongly reduced coordination due to the surface states.

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

Stable isotope ratios in freshwater mussel shells as high resolution recorders of riverine environmental variation

NASA Astrophysics Data System (ADS)

Kukolich, S.; Kendall, C.; Dettman, D. L.

2017-12-01

The geochemical record stored in growth increments of freshwater mussel shells reveals annual to sub-annual changes in environmental conditions during the lifetime of the organism. The carbon, nitrogen, and oxygen stable isotope composition of aragonite shells responds to changes in water chemistry, temperature, streamflow, turbidity, growth rate, size, age, and reproduction. The goals of this study are to determine how stable isotopes can be used to reconstruct the conditions in which the mussels lived and to illuminate any vital effects that might obscure the isotopic record of those conditions. Previous research has suggested that annual δ13C values decrease in older freshwater mussel shells due to lower growth rates and greater incorporation of dietary carbon into the shell with increasing age. However, a high-resolution, seasonal investigation of δ13C, δ15N, and δ18O as they relate to organism age has not yet been attempted in freshwater mussels. A total of 28 Unionid mussels of three different species were collected live in 2011 in the Tennessee River near Paducah, Kentucky, USA. In this study, we analyzed the shell nacre and external organic layers for stable carbon, nitrogen, and oxygen isotope ratios, focusing on growth bands formed between 2006 and 2011. We present a time series of shell δ13C, δ18O, and δ15N values with monthly resolution. We also compare the shell-derived geochemical time series to a time series of the δ13C and δ15N of particulate organic matter, δ13C of DIC, δ18OWater, and water temperature in which the mussels lived. Results show that environmental factors such as water temperature and primary productivity dominate shell chemistry while animal age has little or no effect.

Estimating local, organic, and other price premiums of shell eggs in Hawaii.

PubMed

Loke, Matthew K; Xu, Xun; Leung, PingSun

2016-05-01

Hedonic modeling and retail scanner data were utilized to investigate the influence of local, organic, nutrition benefits, and other attributes of shell eggs on retail price premium in Hawaii. Within a revealed preference framework, the analysis of local and organic attributes, simultaneously, under a single unified setting is important, as such work is highly deficient in the published literature. This paper finds high to moderate price premiums in four key attributes of shell eggs - organic (64%), local (40%), nutrition benefits claimed (33%), and brown shell (18.4%). Large and extra-large sized eggs also experience price premiums over medium sized eggs. With each larger packing size, the estimated coefficients were negative, indicating a price discount, relative to the baseline packing size. However, there is no evidence to support the overwhelming influence of "local" over "organic", as hypothesized in other research work. Overall, the findings in this paper suggest industry producers and retailers should highlight and market effusively the primary attributes of their shell eggs, including "local", to remain competitive in the marketplace. Effective communication channels are crucial to delivering the product information, capturing the attention of consumers, and securing retail sales. © 2016 Poultry Science Association Inc.

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

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.

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.

Limpet Shells from the Aterian Level 8 of El Harhoura 2 Cave (Témara, Morocco): Preservation State of Crossed-Foliated Layers.

PubMed

Nouet, Julius; Chevallard, Corinne; Farre, Bastien; Nehrke, Gernot; Campmas, Emilie; Stoetzel, Emmanuelle; El Hajraoui, Mohamed Abdeljalil; Nespoulet, Roland

2015-01-01

The exploitation of mollusks by the first anatomically modern humans is a central question for archaeologists. This paper focuses on level 8 (dated around ∼ 100 ka BP) of El Harhoura 2 Cave, located along the coastline in the Rabat-Témara region (Morocco). The large quantity of Patella sp. shells found in this level highlights questions regarding their origin and preservation. This study presents an estimation of the preservation status of these shells. We focus here on the diagenetic evolution of both the microstructural patterns and organic components of crossed-foliated shell layers, in order to assess the viability of further investigations based on shell layer minor elements, isotopic or biochemical compositions. The results show that the shells seem to be well conserved, with microstructural patterns preserved down to sub-micrometric scales, and that some organic components are still present in situ. But faint taphonomic degradations affecting both mineral and organic components are nonetheless evidenced, such as the disappearance of organic envelopes surrounding crossed-foliated lamellae, combined with a partial recrystallization of the lamellae. Our results provide a solid case-study of the early stages of the diagenetic evolution of crossed-foliated shell layers. Moreover, they highlight the fact that extreme caution must be taken before using fossil shells for palaeoenvironmental or geochronological reconstructions. Without thorough investigation, the alteration patterns illustrated here would easily have gone unnoticed. However, these degradations are liable to bias any proxy based on the elemental, isotopic or biochemical composition of the shells. This study also provides significant data concerning human subsistence behavior: the presence of notches and the good preservation state of limpet shells (no dissolution/recrystallization, no bioerosion and no abrasion/fragmentation aspects) would attest that limpets were gathered alive with tools by Middle Palaeolithic (Aterian) populations in North Africa for consumption.

Limpet Shells from the Aterian Level 8 of El Harhoura 2 Cave (Témara, Morocco): Preservation State of Crossed-Foliated Layers

PubMed Central

Nouet, Julius; Chevallard, Corinne; Farre, Bastien; Nehrke, Gernot; Campmas, Emilie; Stoetzel, Emmanuelle; El Hajraoui, Mohamed Abdeljalil; Nespoulet, Roland

2015-01-01

The exploitation of mollusks by the first anatomically modern humans is a central question for archaeologists. This paper focuses on level 8 (dated around ∼ 100 ka BP) of El Harhoura 2 Cave, located along the coastline in the Rabat-Témara region (Morocco). The large quantity of Patella sp. shells found in this level highlights questions regarding their origin and preservation. This study presents an estimation of the preservation status of these shells. We focus here on the diagenetic evolution of both the microstructural patterns and organic components of crossed-foliated shell layers, in order to assess the viability of further investigations based on shell layer minor elements, isotopic or biochemical compositions. The results show that the shells seem to be well conserved, with microstructural patterns preserved down to sub-micrometric scales, and that some organic components are still present in situ. But faint taphonomic degradations affecting both mineral and organic components are nonetheless evidenced, such as the disappearance of organic envelopes surrounding crossed-foliated lamellae, combined with a partial recrystallization of the lamellae. Our results provide a solid case-study of the early stages of the diagenetic evolution of crossed-foliated shell layers. Moreover, they highlight the fact that extreme caution must be taken before using fossil shells for palaeoenvironmental or geochronological reconstructions. Without thorough investigation, the alteration patterns illustrated here would easily have gone unnoticed. However, these degradations are liable to bias any proxy based on the elemental, isotopic or biochemical composition of the shells. This study also provides significant data concerning human subsistence behavior: the presence of notches and the good preservation state of limpet shells (no dissolution/recrystallization, no bioerosion and no abrasion/fragmentation aspects) would attest that limpets were gathered alive with tools by Middle Palaeolithic (Aterian) populations in North Africa for consumption. PMID:26376294

Three-dimensional organization of block copolymers on "DNA-minimal" scaffolds.

PubMed

McLaughlin, Christopher K; Hamblin, Graham D; Hänni, Kevin D; Conway, Justin W; Nayak, Manoj K; Carneiro, Karina M M; Bazzi, Hassan S; Sleiman, Hanadi F

2012-03-07

Here, we introduce a 3D-DNA construction method that assembles a minimum number of DNA strands in quantitative yield, to give a scaffold with a large number of single-stranded arms. This DNA frame is used as a core structure to organize other functional materials in 3D as the shell. We use the ring-opening metathesis polymerization (ROMP) to generate block copolymers that are covalently attached to DNA strands. Site-specific hybridization of these DNA-polymer chains on the single-stranded arms of the 3D-DNA scaffold gives efficient access to DNA-block copolymer cages. These biohybrid cages possess polymer chains that are programmably positioned in three dimensions on a DNA core and display increased nuclease resistance as compared to unfunctionalized DNA cages. © 2012 American Chemical Society

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.

Origin and diversity of testate amoebae shell composition: Example of Bullinularia indica living in Sphagnum capillifolium.

PubMed

Delaine, Maxence; Bernard, Nadine; Gilbert, Daniel; Recourt, Philippe; Armynot du Châtelet, Eric

2017-06-01

Testate amoebae are free-living shelled protists that build a wide range of shells with various sizes, shapes, and compositions. Recent studies showed that xenosomic testate amoebae shells could be indicators of atmospheric particulate matter (PM) deposition. However, no study has yet been conducted to assess the intra-specific mineral, organic, and biologic grain diversity of a single xenosomic species in a natural undisturbed environment. This study aims at providing new information about grain selection to develop the potential use of xenosomic testate amoebae shells as bioindicators of the multiple-origin mineral/organic diversity of their proximal environment. To fulfil these objectives, we analysed the shell content of 38 Bullinularia indica individuals, a single xenosomic testate amoeba species living in Sphagnum capillifolium, by scanning electron microscope (SEM) coupled with X-ray spectroscopy. The shells exhibited high diversities of mineral, organic, and biomineral grains, which confirms their capability to recycle xenosomes. Mineral grain diversity and size of B. indica matched those of the atmospheric natural mineral PM deposited in the peatbog. Calculation of grain size sorting revealed a discrete selection of grains agglutinated by B. indica. These results are a first step towards understanding the mechanisms of particle selection by xenosomic testate amoebae in natural conditions. Copyright © 2017 Elsevier GmbH. All rights reserved.

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.

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

NASA Astrophysics Data System (ADS)

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2-]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

One-dimensional organic lead halide perovskites with efficient bluish white-light emission

PubMed Central

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C.; van de Burgt, Lambertus J.; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-01

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C4N2H14PbBr4, in which the edge sharing octahedral lead bromide chains [PbBr4 2−]∞ are surrounded by the organic cations C4N2H14 2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials. PMID:28051092

One-dimensional organic lead halide perovskites with efficient bluish white-light emission.

PubMed

Yuan, Zhao; Zhou, Chenkun; Tian, Yu; Shu, Yu; Messier, Joshua; Wang, Jamie C; van de Burgt, Lambertus J; Kountouriotis, Konstantinos; Xin, Yan; Holt, Ethan; Schanze, Kirk; Clark, Ronald; Siegrist, Theo; Ma, Biwu

2017-01-04

Organic-inorganic hybrid metal halide perovskites, an emerging class of solution processable photoactive materials, welcome a new member with a one-dimensional structure. Herein we report the synthesis, crystal structure and photophysical properties of one-dimensional organic lead bromide perovskites, C 4 N 2 H 14 PbBr 4 , in which the edge sharing octahedral lead bromide chains [PbBr 4   2- ] ∞ are surrounded by the organic cations C 4 N 2 H 14   2+ to form the bulk assembly of core-shell quantum wires. This unique one-dimensional structure enables strong quantum confinement with the formation of self-trapped excited states that give efficient bluish white-light emissions with photoluminescence quantum efficiencies of approximately 20% for the bulk single crystals and 12% for the microscale crystals. This work verifies once again that one-dimensional systems are favourable for exciton self-trapping to produce highly efficient below-gap broadband luminescence, and opens up a new route towards superior light emitters based on bulk quantum materials.

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.

Exploring the utility of high resolution "nano-" computed tomography imaging to place quantitative constraints on shell biometric changes in marine pteropods in response to ocean acidification

NASA Astrophysics Data System (ADS)

Eagle, R.; Howes, E.; Lischka, S.; Rudolph, R.; Büdenbender, J.; Bijma, J.; Gattuso, J. P.; Riebesell, U.

2014-12-01

Understanding and quantifying the response of marine organisms to present and future ocean acidification remains a major challenge encompassing observations on single species in culture and scaling up to the ecosystem and global scale. Understanding calcification changes in culture experiments designed to simulate present and future ocean conditions under potential CO2 emissions scenarios, and especially detecting the likely more subtle changes that may occur prior to the onset of more extreme ocean acidification, depends on the tools available. Here we explore the utility of high-resolution computed tomography (nano-CT) to provide quantitative biometric data on field collected and cultured marine pteropods, using the General Electric Company Phoenix Nanotom S Instrument. The technique is capable of quantitating the whole shell of the organism, allowing shell dimensions to be determined as well as parameters such as average shell thickness, the variation in thickness across the whole shell and in localized areas, total shell volume and surface area and when combined with weight measurements shell density can be calculated. The potential power of the technique is the ability to derive these parameters even on very small organisms less than 1 millimeter in size. Tuning the X-ray strength of the instrument allows organic material to be excluded from the analysis. Through replicate analysis of standards, we assess the reproducibility of data, and by comparison with dimension measurements derived from light microscopy we assess the accuracy of dimension determinations. We present results from historical and modern pteropod populations from the Mediterranean and cultured polar pteropods, resolving statistically significant differences in shell biometrics in both cases that may represent responses to ocean acidification.

Ocean acidification and temperature increase impact mussel shell shape and thickness: problematic for protection?

PubMed

Fitzer, Susan C; Vittert, Liberty; Bowman, Adrian; Kamenos, Nicholas A; Phoenix, Vernon R; Cusack, Maggie

2015-11-01

Ocean acidification threatens organisms that produce calcium carbonate shells by potentially generating an under-saturated carbonate environment. Resultant reduced calcification and growth, and subsequent dissolution of exoskeletons, would raise concerns over the ability of the shell to provide protection for the marine organism under ocean acidification and increased temperatures. We examined the impact of combined ocean acidification and temperature increase on shell formation of the economically important edible mussel Mytilus edulis. Shell growth and thickness along with a shell thickness index and shape analysis were determined. The ability of M. edulis to produce a functional protective shell after 9 months of experimental culture under ocean acidification and increasing temperatures (380, 550, 750, 1000 μatm pCO 2, and 750, 1000 μatm pCO 2 + 2°C) was assessed. Mussel shells grown under ocean acidification conditions displayed significant reductions in shell aragonite thickness, shell thickness index, and changes to shell shape (750, 1000 μatm pCO 2) compared to those shells grown under ambient conditions (380 μatm pCO 2). Ocean acidification resulted in rounder, flatter mussel shells with thinner aragonite layers likely to be more vulnerable to fracture under changing environments and predation. The changes in shape presented here could present a compensatory mechanism to enhance protection against predators and changing environments under ocean acidification when mussels are unable to grow thicker shells. Here, we present the first assessment of mussel shell shape to determine implications for functional protection under ocean acidification.

Spatial analysis of biomineralization associated gene expression from the mantle organ of the pearl oyster Pinctada maxima

PubMed Central

2011-01-01

Background Biomineralization is a process encompassing all mineral containing tissues produced within an organism. One of the most dynamic examples of this process is the formation of the mollusk shell, comprising a variety of crystal phases and microstructures. The organic component incorporated within the shell is said to dictate this architecture. However general understanding of how this process is achieved remains ambiguous. The mantle is a conserved organ involved in shell formation throughout molluscs. Specifically the mantle is thought to be responsible for secreting the protein component of the shell. This study employs molecular approaches to determine the spatial expression of genes within the mantle tissue to further the elucidation of the shell biomineralization. Results A microarray platform was custom generated (PmaxArray 1.0) from the pearl oyster Pinctada maxima. PmaxArray 1.0 consists of 4992 expressed sequence tags (ESTs) originating from mantle tissue. This microarray was used to analyze the spatial expression of ESTs throughout the mantle organ. The mantle was dissected into five discrete regions and analyzed for differential gene expression with PmaxArray 1.0. Over 2000 ESTs were determined to be differentially expressed among the tissue sections, identifying five major expression regions. In situ hybridization validated and further localized the expression for a subset of these ESTs. Comparative sequence similarity analysis of these ESTs revealed a number of the transcripts were novel while others showed significant sequence similarities to previously characterized shell related genes. Conclusions This investigation has mapped the spatial distribution for over 2000 ESTs present on PmaxArray 1.0 with reference to specific locations of the mantle. Expression profile clusters have indicated at least five unique functioning zones in the mantle. Three of these zones are likely involved in shell related activities including formation of nacre, periostracum and calcitic prismatic microstructure. A number of novel and known transcripts have been identified from these clusters. The development of PmaxArray 1.0, and the spatial map of its ESTs expression in the mantle has begun characterizing the molecular mechanisms linking the organics and inorganics of the molluscan shell. PMID:21936921

Bioluminescent signals spatially amplified by wavelength-specific diffusion through the shell of a marine snail.

PubMed

Deheyn, Dimitri D; Wilson, Nerida G

2011-07-22

Some living organisms produce visible light (bioluminescence) for intra- or interspecific visual communication. Here, we describe a remarkable bioluminescent adaptation in the marine snail Hinea brasiliana. This species produces a luminous display in response to mechanical stimulation caused by encounters with other motile organisms. The light is produced from discrete areas on the snail's body beneath the snail's shell, and must thus overcome this structural barrier to be viewed by an external receiver. The diffusion and transmission efficiency of the shell is greater than a commercial diffuser reference material. Most strikingly, the shell, although opaque and pigmented, selectively diffuses the blue-green wavelength of the species bioluminescence. This diffusion generates a luminous display that is enlarged relative to the original light source. This unusual shell thus allows spatially amplified outward transmission of light communication signals from the snail, while allowing the animal to remain safely inside its hard protective shell.

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.

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

A Complete Structural Inventory of the Mycobacterial Microcompartment Shell Proteins Constrains Models of Global Architecture and Transport*

PubMed Central

Mallette, Evan

2017-01-01

Bacterial microcompartments are bacterial analogs of eukaryotic organelles in that they spatially segregate aspects of cellular metabolism, but they do so by building not a lipid membrane but a thin polyhedral protein shell. Although multiple shell protein structures are known for several microcompartment types, additional uncharacterized components complicate systematic investigations of shell architecture. We report here the structures of all four proteins proposed to form the shell of an uncharacterized microcompartment designated the Rhodococcus and Mycobacterium microcompartment (RMM), which, along with crystal interactions and docking studies, suggests possible models for the particle's vertex and edge organization. MSM0272 is a typical hexameric β-sandwich shell protein thought to form the bulk of the facet. MSM0273 is a pentameric β-barrel shell protein that likely plugs the vertex of the particle. MSM0271 is an unusual double-ringed bacterial microcompartment shell protein whose rings are organized in an offset position relative to all known related proteins. MSM0275 is related to MSM0271 but self-organizes as linear strips that may line the facet edge; here, the presence of a novel extendable loop may help ameliorate poor packing geometry of the rigid main particle at the angled edges. In contrast to previously characterized homologs, both of these proteins show closed pores at both ends. This suggests a model where key interactions at the vertex and edges are mediated at the inner layer of the shell by MSM0271 (encircling MSM0273) and MSM0275, and the facet is built from MSM0272 hexamers tiling in the outer layer of the shell. PMID:27927988

A Complete Structural Inventory of the Mycobacterial Microcompartment Shell Proteins Constrains Models of Global Architecture and Transport.

PubMed

Mallette, Evan; Kimber, Matthew S

2017-01-27

Bacterial microcompartments are bacterial analogs of eukaryotic organelles in that they spatially segregate aspects of cellular metabolism, but they do so by building not a lipid membrane but a thin polyhedral protein shell. Although multiple shell protein structures are known for several microcompartment types, additional uncharacterized components complicate systematic investigations of shell architecture. We report here the structures of all four proteins proposed to form the shell of an uncharacterized microcompartment designated the Rhodococcus and Mycobacterium microcompartment (RMM), which, along with crystal interactions and docking studies, suggests possible models for the particle's vertex and edge organization. MSM0272 is a typical hexameric β-sandwich shell protein thought to form the bulk of the facet. MSM0273 is a pentameric β-barrel shell protein that likely plugs the vertex of the particle. MSM0271 is an unusual double-ringed bacterial microcompartment shell protein whose rings are organized in an offset position relative to all known related proteins. MSM0275 is related to MSM0271 but self-organizes as linear strips that may line the facet edge; here, the presence of a novel extendable loop may help ameliorate poor packing geometry of the rigid main particle at the angled edges. In contrast to previously characterized homologs, both of these proteins show closed pores at both ends. This suggests a model where key interactions at the vertex and edges are mediated at the inner layer of the shell by MSM0271 (encircling MSM0273) and MSM0275, and the facet is built from MSM0272 hexamers tiling in the outer layer of the shell. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

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

In-depth proteomic analysis of a mollusc shell: acid-soluble and acid-insoluble matrix of the limpet Lottia gigantea

PubMed Central

2012-01-01

Background Invertebrate biominerals are characterized by their extraordinary functionality and physical properties, such as strength, stiffness and toughness that by far exceed those of the pure mineral component of such composites. This is attributed to the organic matrix, secreted by specialized cells, which pervades and envelops the mineral crystals. Despite the obvious importance of the protein fraction of the organic matrix, only few in-depth proteomic studies have been performed due to the lack of comprehensive protein sequence databases. The recent public release of the gastropod Lottia gigantea genome sequence and the associated protein sequence database provides for the first time the opportunity to do a state-of-the-art proteomic in-depth analysis of the organic matrix of a mollusc shell. Results Using three different sodium hypochlorite washing protocols before shell demineralization, a total of 569 proteins were identified in Lottia gigantea shell matrix. Of these, 311 were assembled in a consensus proteome comprising identifications contained in all proteomes irrespective of shell cleaning procedure. Some of these proteins were similar in amino acid sequence, amino acid composition, or domain structure to proteins identified previously in different bivalve or gastropod shells, such as BMSP, dermatopontin, nacrein, perlustrin, perlucin, or Pif. In addition there were dozens of previously uncharacterized proteins, many containing repeated short linear motifs or homorepeats. Such proteins may play a role in shell matrix construction or control of mineralization processes. Conclusions The organic matrix of Lottia gigantea shells is a complex mixture of proteins comprising possible homologs of some previously characterized mollusc shell proteins, but also many novel proteins with a possible function in biomineralization as framework building blocks or as regulatory components. We hope that this data set, the most comprehensive available at present, will provide a platform for the further exploration of biomineralization processes in molluscs. PMID:22540284

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.

The Triassic upwelling system of Arctic Alaska

NASA Astrophysics Data System (ADS)

Yurchenko, I.; Graham, S. A.

2017-12-01

The Middle to Upper Triassic Shublik Formation of Arctic Alaska is a laterally and vertically heterogeneous rock unit that has been analyzed both in outcrop and in the subsurface. The Shublik Formation sediments are distinguished by a characteristic set of lithologies that include glauconitic, phosphatic, organic-rich, and cherty facies consistent with a coastal upwelling zone deposition interpretation. It is often recognized by abundance of impressions and shells of distinctive Triassic bivalves. To understand main controls on lithofacies distributions, this study reviews and refines lithologic and paleoenvironmental interpretations of the Shublik Formation, and incorporates the newly acquired detailed geochemical analyses of two complete Shublik cores. This work focuses on organic geochemistry (analyses of biomarkers and diamondoids), chemostratigraphy (hand-held XRF), and iron speciation analysis to reconstruct paleoproductivity and redox conditions. Based on the available evidence, during Shublik deposition, an upwelling-influenced open shelf resulted in high nutrient supply that stimulated algal blooms leading to high net organic productivity, reduced water transparency, oxygen deficiency, and water column stratification. Evidence of such eutrophic conditions is indicated by the lack of photic benthic organisms, bioturbation and trace fossils, and dominance of the monospecific light-independent epibenthic bivalves. The flat, subcircular, thin shells of these carbonate-secreting organisms allowed them to adapt to dysoxic conditions, and float on soft, soupy, muddy substrate. The distinctive clay- and organic-rich facies with abundant bivalves occurred on the mid to outer stable broad shelf, and were deposited when organic productivity at times overlapped with periods of increased siliciclastic input controlled by sea level and changes in local sediment dispersal systems, and therefore are more spatially and temporally localized than the widespread clay-poor facies. The overall lithofacies distribution in the Shublik Formation can therefore be described by the interplay of sea level, detrital sediment input, local bathymetry and hydrodynamic conditions without requiring changes in organic sources input or redox conditions.

Impacts of Near-Future Ocean Acidification and Warming on the Shell Mechanical and Geochemical Properties of Gastropods from Intertidal to Subtidal Zones.

PubMed

Leung, Jonathan Y S; Connell, Sean D; Nagelkerken, Ivan; Russell, Bayden D

2017-11-07

Many marine organisms produce calcareous shells as the key structure for defense, but the functionality of shells may be compromised by ocean acidification and warming. Nevertheless, calcifying organisms may adaptively modify their shell properties in response to these impacts. Here, we examined how reduced pH and elevated temperature affect shell mechanical and geochemical properties of common grazing gastropods from intertidal to subtidal zones. Given the greater environmental fluctuations in the intertidal zone, we hypothesized that intertidal gastropods would exhibit more plastic responses in shell properties than subtidal gastropods. Overall, three out of five subtidal gastropods produced softer shells at elevated temperature, while intertidal gastropods maintained their shell hardness at both elevated pCO 2 (i.e., reduced pH) and temperature. Regardless of pH and temperature, degree of crystallization was maintained (except one subtidal gastropod) and carbonate polymorph remained unchanged in all tested species. One intertidal gastropod produced less soluble shells (e.g., higher calcite/aragonite) in response to reduced pH. In contrast, subtidal gastropods produced only aragonite which has higher solubility than calcite. Overall, subtidal gastropods are expected to be more susceptible than intertidal gastropods to shell dissolution and physical damage under future seawater conditions. The increased vulnerability to shell dissolution and predation could have serious repercussions for their survival and ecological contributions in the future subtidal environment.

Construction of Matryoshka-type structures from supercharged protein nanocages.

PubMed

Beck, Tobias; Tetter, Stephan; Künzle, Matthias; Hilvert, Donald

2015-01-12

Designing nanoscaled hierarchical structures with increasing levels of complexity is challenging. Here we show that electrostatic interactions between two complementarily supercharged protein nanocages can be effectively utilized to create nested Matryoshka-type structures. Cage-within-cage complexes containing spatially ordered iron oxide nanoparticles spontaneously self-assemble upon mixing positively supercharged ferritin compartments with AaLS-13, a larger shell-forming protein with a negatively supercharged lumen. Exploiting engineered Coulombic interactions and protein dynamics in this way opens up new avenues for creating hierarchically organized supramolecular assemblies for application as delivery vehicles, reaction chambers, and artificial organelles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic Rankine cycle receiver development

NASA Technical Reports Server (NTRS)

Haskins, H. J.

1981-01-01

The selected receiver concept is a direct-heated, once-through, monotube boiler operated at supercritical pressure. The cavity is formed by a cylindrical copper shell and backwall, with stainless steel tubing brazed to the outside surface. This core is surrounded by lightweight refractory insulation, load-bearing struts, and an outer case. The aperture plate is made of copper to provide long life by conduction and reradiation of heat away from the aperture lip. The receiver thermal efficiency is estimated to be 97 percent at rated conditions (energy transferred to toluene divided by energy incident on aperture opening). Development of the core manufacturing and corrosion protection methods is complete.

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...

Hexakis(3,6-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)cyclohexane: Closed-shell [6]Radialene or Open-shell Hexa-radicaloid?

PubMed

Wu, Jishan; Feng, Jiaqi; Gopalakrishna, Tullimilli Y; Phan, Hoa

2018-04-19

We report a star-shaped hexaquinocyclohexane molecule 4c, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5 ± 4.3 kJ/mol at room temperature from the hexa-radical form 4o to the contorted [6]radialene form 4c, because the transformation need overcome large steric repulsion between the neighbouring phenoxyl units. Compound 4c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9%. This study demonstrated the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Finite Element Analysis of Crack-Path Selection in a Brick and Mortar Structure

NASA Astrophysics Data System (ADS)

Sarrafi-Nour, Reza; Manoharan, Mohan; Johnson, Curtis A.

Many natural composite materials rely on organized architectures that span several length scales. The structures of natural shells such as nacre (mother-of-pearl) and conch are prominent examples of such organizations where the calcium carbonate platelets, the main constituent of natural shells, are held together in an organized fashion within an organic matrix. At one or multiple length scales, these organized arrangements often resemble a brick-and-mortar structure, with calcium carbonate platelets acting as bricks connected through the organic mortar phase.

Lipids from the nacreous and prismatic layers of two Pteriomorpha Mollusc shells

NASA Astrophysics Data System (ADS)

Farre, B.; Dauphin, Y.

2009-04-01

Mollusc shells are the best-known Ca-carbonate biominerals. They are commonly described as a mineralized two layered structure: an outer layer composed of calcite prismatic units, and an internal layer composed of tablets of aragonite: the nacreous layer. An external organic layer (periostracum) is present in most taxa. However, the most common structure in the Mollusc shell is the aragonite crossed lamellar layer, but aragonite prisms, calcite foliated layers and homogeneous layers have been also described by Boggild (1930) in all the Mollusc orders. Since, more detailed descriptions of Bivalve shells have been done (Taylor et al., 1969, 1973). Despite the nacroprismatic arrangement is rare, calcite prismatic and aragonite nacreous layers are the best studied because of their simple 3D structure and large units. Among these Molluscs, some Bivalve species composed of these two layers are of commercial interest, such as the pearl oyster, Pinctada margaritifera, cultivated in French Polynesia to produce black pearls. It is well established that Mollusc shells are composite structures of organic and inorganic components (Hatchett, 1799; Grégoire et al., 1955; Beedham, 1958; Simkiss, 1965; Mutvei, 1969; Cuif et al., 1980; Berman et al., 1993; Kobayashi and Samata, 2006). Numerous studies are concerned with the organic matrix of the shell. Organic components are commonly obtained after a strong or mild decalcification process. They are said to consist of both a soluble and insoluble fraction. The main part of studies is dedicated to the soluble components, and among them, proteins (Grégoire et al., 1955; Grégoire, 1961; Krampitz et al., 1976; Samata et al., 1980, 2004; Weiner, 1983; Miyamoto et al., 2006). Despite the pioneering work of Wada (1980) sugars are usually neglected despite their role in biomineralization. The third component of the organic matrix of calcareous biominerals is lipids. To date, there is a paucity of information concerning the presence, abundance and composition of these components in Mollusc shells. Goulletquer and Wolowicz (1989) have estimated that proteins represent 90% of the organic matrix of the shell, carbohydrates vary from 0.15 to 0.29%, while lipids vary from 0.8 to 2.9%. Fatty acids, cholesterol, phytadienes and ketones have been described in modern and fossil shells (Cobabe and Pratt, 1995). Using a procedure to extract intra- and intercrystalline organic matrices, Collins et al. (1995) have detected n-alkanes, n-alcohols, fatty acids and sterols in modern shells. It is suggested that the contents and ratios of these components are dependant on the environment and phylogeny. Lipids of the nacreous layer of Pinctada are diverse, with cholesterol, fatty acids, triglycerides and other unknown components (Rousseau et al., 2006). It has been established that the main part of the soluble organic matrices of the nacreous layer is composed of acidic proteins (Samata, 1988, 1990), whereas the prismatic layer of Pinna is mainly composed of acidic and sulphated polysaccharides (Dauphin, 2002; Dauphin et al., 2003). The amino acid compositions of the two layers are also different (Samata, 1990). Because the organic matrices extracted from the aragonite nacre and calcite prisms are the best known materials, the lipids extracted from the calcite prisms of Pinna nobilis and Pinctada margaritifera and the aragonite nacre of P. margaritifera have been chosen as test material for characterisation of the lipid fraction of molusk shells. The nacreous layer of Pinctada is thick,whereas its prismatic layer is thin, and the prisms display complex structures. On the opposite, the calcitic prismatic layer of Pinna is thick, with no intraprismatic membranes, and its nacreous layer is thin and present only in the oldest part of the shell. Moreover, these layers have a simple geometry so that some organic components (membranes, wall…) said to be insoluble, are clearly visible. Lipids were extracted from the calcite prismatic and aragonite nacreous layer of two mollusc shells thanks organic solvents. Two methods were used for the characterisation of the lipid obtaiened Fourier Tranform Infrared Spectrometry and thin layed chromatography. Fourier Transform Infrared Spectrometry shows that lipids are present in both samples, but they are not similar. Thin layer chromatography confirms that lipids are different in the two studied layers, so that it may be suggested they are species-dependant, but also structure-dependant. Although not yet deciphered, their role in biomineralization and fossilisation processes is probably important.

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.

Characteristics of global organic matrix in normal and pimpled chicken eggshells.

PubMed

Liu, Z; Song, L; Zhang, F; He, W; Linhardt, R J

2017-10-01

The organic matrix from normal and pimpled calcified chicken eggshells were dissociated into acid-insoluble, water-insoluble, and facultative-soluble (both acid- and water-soluble) components, to understand the influence of shell matrix on eggshell qualities. A linear correlation was shown among these 3 matrix components in normal eggshells but was not observed in pimpled eggshells. In pimpled eggshells, the percentage contents of all 4 groups of matrix (the total matrix, acid-insoluble matrix, water-insoluble matrix, and facultative-soluble matrix) were significantly higher than that in normal eggshells. The amounts of both total matrix and acid-insoluble matrix in individual pimpled calcified shells were high, even though their weight was much lower than a normal eggshell. In both normal and pimpled eggshells, the calcified eggshell weight and shell thickness significantly and positively correlated with the amounts of all 4 groups of matrix in an individual calcified shell. In normal eggshells, the calcified shell thickness and shell breaking strength showed no significant correlations with the percentage contents of all 4 groups of matrix. In normal eggshells, only the shell membrane weight significantly correlated with the constituent ratios of both acid-insoluble matrix and facultative-soluble matrix in the whole matrix. In pimpled eggshells, 3 variables (calcified shell weight, shell thickness, and breaking strength) were significantly correlated with the constituent proportions of both acid-insoluble matrix and facultative-matrix. This study suggests that mechanical properties of normal eggshells may not linearly depend on the organic matrix content in the calcified eggshells and that pimpled eggshells might result by the disequilibrium enrichment of some proteins with negative effects. © 2017 Poultry Science Association Inc.

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.

Probing the structural flexibility of MOFs by constructing metal oxide@MOF-based heterostructures for size-selective photoelectrochemical response

NASA Astrophysics Data System (ADS)

Zhan, Wenwen; He, Yue; Guo, Jiangbin; Chen, Luning; Kong, Xiangjian; Zhao, Haixia; Kuang, Qin; Xie, Zhaoxiong; Zheng, Lansun

2016-07-01

It is becoming a challenge to achieve simpler characterization and wider application of flexible metal organic frameworks (MOFs) exhibiting the gate-opening or breathing behavior. Herein, we designed an intelligent MOF-based system where the gate-opening or breathing behavior of MOFs can be facially visualized in solution. Two types of metal oxide@MOF core-shell heterostructures, ZnO@ZIF-7 and ZnO@ZIF-71, were prepared using ZnO nanorods as self-sacrificial templates. The structural flexibility of both the MOFs can be easily judged from the distinct molecular-size-related formation modes and photoelectrochemical performances between the two ZnO@ZIF heterostructures. Moreover, the rotational dynamics of the flexible parts of ZIF-7 were studied by analyzing the intrinsic physical properties, such as dielectric constants, of the structure. The present work reminds us to pay particular attention to the influences of the structural flexibility of MOFs on the structure and properties of MOF-involved heterostructures in future studies.It is becoming a challenge to achieve simpler characterization and wider application of flexible metal organic frameworks (MOFs) exhibiting the gate-opening or breathing behavior. Herein, we designed an intelligent MOF-based system where the gate-opening or breathing behavior of MOFs can be facially visualized in solution. Two types of metal oxide@MOF core-shell heterostructures, ZnO@ZIF-7 and ZnO@ZIF-71, were prepared using ZnO nanorods as self-sacrificial templates. The structural flexibility of both the MOFs can be easily judged from the distinct molecular-size-related formation modes and photoelectrochemical performances between the two ZnO@ZIF heterostructures. Moreover, the rotational dynamics of the flexible parts of ZIF-7 were studied by analyzing the intrinsic physical properties, such as dielectric constants, of the structure. The present work reminds us to pay particular attention to the influences of the structural flexibility of MOFs on the structure and properties of MOF-involved heterostructures in future studies. Electronic supplementary information (ESI) available: Experimental details, XRD patterns and SEM images of products in other reactions, concentration-dependent photocurrent responses, and supplementary data of dielectric measurements. See DOI: 10.1039/c6nr02257j

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

NASA Astrophysics Data System (ADS)

Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better recorder of diet than is the insoluble shell organic carbon. Because the systematic fractionation of carbon isotopes within the snail is temperature dependent, the δ 13C of the shell could provide an independent technique for estimating paleotemperature changes.

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.

Atom Probe Tomographic Mapping Directly Reveals the Atomic Distribution of Phosphorus in Resin Embedded Ferritin

NASA Astrophysics Data System (ADS)

Perea, Daniel E.; Liu, Jia; Bartrand, Jonah; Dicken, Quinten; Thevuthasan, S. Theva; Browning, Nigel D.; Evans, James E.

2016-02-01

Here we report the atomic-scale analysis of biological interfaces within the ferritin protein using atom probe tomography that is facilitated by an advanced specimen preparation approach. Embedding ferritin in an organic polymer resin lacking nitrogen provided chemical contrast to visualise atomic distributions and distinguish the inorganic-organic interface of the ferrihydrite mineral core and protein shell, as well as the organic-organic interface between the ferritin protein shell and embedding resin. In addition, we definitively show the atomic-scale distribution of phosphorus as being at the surface of the ferrihydrite mineral with the distribution of sodium mapped within the protein shell environment with an enhanced distribution at the mineral/protein interface. The sample preparation method is robust and can be directly extended to further enhance the study of biological, organic and inorganic nanomaterials relevant to health, energy or the environment.

Atom Probe Tomographic Mapping Directly Reveals the Atomic Distribution of Phosphorus in Resin Embedded Ferritin

PubMed Central

Perea, Daniel E.; Liu, Jia; Bartrand, Jonah; Dicken, Quinten; Thevuthasan, S. Theva; Browning, Nigel D.; Evans, James E.

2016-01-01

Here we report the atomic-scale analysis of biological interfaces within the ferritin protein using atom probe tomography that is facilitated by an advanced specimen preparation approach. Embedding ferritin in an organic polymer resin lacking nitrogen provided chemical contrast to visualise atomic distributions and distinguish the inorganic-organic interface of the ferrihydrite mineral core and protein shell, as well as the organic-organic interface between the ferritin protein shell and embedding resin. In addition, we definitively show the atomic-scale distribution of phosphorus as being at the surface of the ferrihydrite mineral with the distribution of sodium mapped within the protein shell environment with an enhanced distribution at the mineral/protein interface. The sample preparation method is robust and can be directly extended to further enhance the study of biological, organic and inorganic nanomaterials relevant to health, energy or the environment. PMID:26924804

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

Tunable Non-Thermal Distribution of Hot Electrons in a Semiconductor Injected from a Plasmonic Gold Nanostructure.

PubMed

Cushing, Scott Kevin; Chen, Chih-Jung; Dong, Chung Li; Kong, Xiang-Tian; Govorov, Alexander O; Liu, Ru-Shi; Wu, Nianqiang

2018-06-26

For semiconductors photosensitized with organic dyes or quantum dots, transferred electrons are usually considered thermalized at the conduction band edge. This study suggests that the electrons injected from a plasmonic metal into a thin semiconductor shell can be non-thermal with energy up to the plasmon frequency. In other words, the electrons injected into the semiconductor are still hot carriers. Photomodulated x-ray absorption measurements of the Ti L 2,3 edge are compared before and after excitation of the plasmon in Au@TiO 2 core shell nanoparticles. Comparison with theoretical predictions of the x-ray absorption, which include the heating and state-filling effects from injected hot carriers, suggest that the electrons transferred from the plasmon remain non-thermal in the ~10 nm TiO 2 shell, due in part to a slow trapping in defect states. By repeating the measurements for spherical, rod-like, and star-like metal nanoparticles, the magnitude of the non-thermal distribution, peak energy, and number of injected hot electrons are confirmed to be tuned by the plasmon frequency and the sharp corners of the plasmonic nanostructure. The results suggest that plasmonic photosensitizers can not only extend the sunlight absorption spectral range of semiconductor-based devices, but could also result in increased open circuit voltages and elevated thermodynamic driving forces for solar fuel generation in photoelectrochemical cells.

Modulation of biogenic amines content by poly(propylene imine) dendrimers in rats.

PubMed

Ciepluch, Karol; Ziemba, Barbara; Janaszewska, Anna; Appelhans, Dietmar; Klajnert, Barbara; Bryszewska, Maria; Fogel, Wiesława Agnieszka

2012-09-01

Biogenic amines and polyamines participate in all vital organism functions, their levels being important function determinants. Studies were performed to check whether repeated administration of poly(propylene imine) (PPI) dendrimers, synthetic macromolecules with diaminobutane core, and peripheral primary amine groups, may influence the endogenous level of amines, as represented by the two of them: spermidine, a natural derivative of diaminobutane, and histamine. The experiment was carried out on Wistar rats. Fourth generation PPI dendrimer, as well as maltotriose-modified fourth generation PPI dendrimers with (a) cationic open sugar shell and (b) neutral dense sugar shell that possess a higher biocompatibility, was used. Applying the combination of column chromatography on Cellex P and spectrofluorimetric assays of o-phthaldialdehyde, the final amine condensation products were employed to analyze tissue spermidine and histamine outside the central nervous system. Furthermore, radioenzymatic assay was used to measure histamine levels in the brain. The obtained results indicate that in some tissues, the endogenous concentrations of histamine and spermidine may be affected by dendrimers depending on their dose and type of dendrimers.

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

Biofiltration of methanol in an organic biofilter using peanut shells as medium.

PubMed

Ramirez-Lopez, E M; Corona-Hernandez, J; Avelar-Gonzalez, F J; Omil, F; Thalasso, F

2010-01-01

Biofiltration consists of a filter-bed of organic matter serving both as carrier for the active biomass and as nutrient supply, through which the polluted gas passes. The selection of a suitable medium material is of major importance to ensure optimum biofilter efficiency. Peanut shells are an agricultural byproduct locally available in large quantities at a low price in most tropical and sub-tropical countries. A previous study showed that peanut shells are physically and chemically suitable for biofiltration. This paper presents the results obtained during a six month biofiltration experiment using peanut shells as medium and methanol as air pollutant. It is shown that peanut shells are potentially suitable as biofiltration medium, since degradation rates of up to 30 kg MeOH/m(3)d with an empty bed residence time of 19s was obtained. The biofilter showed a good resistance to shock load and no operational problems were observed.

Synthesis of Co/MFe(2)O(4) (M = Fe, Mn) Core/Shell Nanocomposite Particles.

PubMed

Peng, Sheng; Xie, Jin; Sun, Shouheng

2008-01-01

Monodispersed cobalt nanoparticles (NPs) with controllable size (8-14 nm) have been synthesized using thermal decomposition of dicobaltoctacarbonyl in organic solvent. The as-synthesized high magnetic moment (125 emu/g) Co NPs are dispersible in various organic solvents, and can be easily transferred into aqueous phase by surface modification using phospholipids. However, the modified hydrophilic Co NPs are not stable as they are quickly oxidized, agglomerated in buffer. Co NPs are stabilized by coating the MFe(2)O(4) (M = Fe, Mn) ferrite shell. Core/shell structured bimagnetic Co/MFe(2)O(4) nanocomposites are prepared with tunable shell thickness (1-5 nm). The Co/MFe(2)O(4) nanocomposites retain the high magnetic moment density from the Co core, while gaining chemical and magnetic stability from the ferrite shell. Comparing to Co NPs, the nanocomposites show much enhanced stability in buffer solution at elevated temperatures, making them promising for biomedical applications.

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.

Shell growth and environmental control of methanophyllic Thyasirid bivalves from Svalbard cold seeps

NASA Astrophysics Data System (ADS)

Carroll, Michael; Åström, Emmelie; Ambrose, William; Locke, William; Oliver, Graham; Hong, Wei-Li; Carroll, JoLynn

2016-04-01

The analysis of molluscan shell material (sclerochronology) can provide information about an organism's age, growth history, and environmental conditions during its lifetime. Bivalve molluscs are common members of hydrothermal vents and methane cold seeps communities where, supported by chemosynthetic symbionts, they can reach high density and biomass. But little is known about methane-associated bivalve populations inhabiting high-Arctic cold seeps, and sclerochronological analysis of methane-influenced bivalves is rare. We measured growth rates and elemental and isotopic shell signatures in a newly discovered species of bivalve (Thyasiridae) from cold seeps at 350-390m depth southwest of Svalbard. First discovered in 2014, recently described shells of Thyasira capitanea sp.nov. were found at 2 independent seep systems in Storfjordrenna. Mean shell carbon isotopic ratios from inorganic δ13C (mean = -4.8‰) and organic δ13C (mean = -26.9‰) fractions clearly indicate a methane influenced habitat and food source for these organisms. Shell mineral ratios (Li/Ca, Mg/Ca, Mn/Ca, Fe/Ca, Sr/Ca, Ba/Ca, Pb/Ca) sampled along the axis of growth with laser-ablated ICP-MS exhibit variability through time and between sites, suggesting that concentrations of these elements that may be affected by methane emissions. The mineralogical data also elucidates the internal pattern of shell deposition and growth checks, and combined with the isotopic and growth rate data, enables us to interpret the temporal history of methane release from these locations.

A shell regeneration assay to identify biomineralization candidate genes in mytilid mussels.

PubMed

Hüning, Anne K; Lange, Skadi M; Ramesh, Kirti; Jacob, Dorrit E; Jackson, Daniel J; Panknin, Ulrike; Gutowska, Magdalena A; Philipp, Eva E R; Rosenstiel, Philip; Lucassen, Magnus; Melzner, Frank

2016-06-01

Biomineralization processes in bivalve molluscs are still poorly understood. Here we provide an analysis of specifically expressed sequences from a mantle transcriptome of the blue mussel, Mytilus edulis. We then developed a novel, integrative shell injury assay to test, whether biomineralization candidate genes highly expressed in marginal and pallial mantle could be induced in central mantle tissue underlying the damaged shell areas. This experimental approach makes it possible to identify gene products that control the chemical micro-environment during calcification as well as organic matrix components. This is unlike existing methodological approaches that work retroactively to characterize calcification relevant molecules and are just able to examine organic matrix components that are present in completed shells. In our assay an orthogonal array of nine 1mm holes was drilled into the left valve, and mussels were suspended in net cages for 20, 29 and 36days to regenerate. Structural observations using stereo-microscopy, SEM and Raman spectroscopy revealed organic sheet synthesis (day 20) as the first step of shell-repair followed by the deposition of calcite crystals (days 20 and 29) and aragonite tablets (day 36). The regeneration period was characterized by time-dependent shifts in gene expression in left central mantle tissue underlying the injured shell, (i) increased expression of two tyrosinase isoforms (TYR3: 29-fold and TYR6: 5-fold) at day 20 with a decline thereafter, (ii) an increase in expression of a gene encoding a nacrein-like protein (max. 100-fold) on day 29. The expression of an acidic Asp-Ser-rich protein was enhanced during the entire regeneration process. This proof-of-principle study demonstrates that genes that are specifically expressed in pallial and marginal mantle tissue can be induced (4 out of 10 genes) in central mantle following experimental injury of the overlying shell. Our findings suggest that regeneration assays can be used systematically to better characterize gene products that are essential for distinct phases of the shell formation process, particularly those that are not incorporated into the organic shell matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Sclerochronology of Holocene oyster shells (Crassostrea gigas) from the West Coast of Bohai Sea, China

NASA Astrophysics Data System (ADS)

Fan, C.; Koeniger, P.; Wang, H.; Frechen, M.

2009-04-01

Sclerochronology, the study of periodic increments in skeletal organisms, can decipher the life history and environmental records preserved in fossil shells. Although there have been a number of studies that apply isotopic analyses to shells in open ocean and fresh water, investigations for brackish environments are rare. One of the common inhabitants in estuaries is the Crassostrea oyster. Kirby et al. (1998) demonstrated a close correspondence between the ligamental increments of convex and concave bands and yearly ^18O cycles; Andrus and Crowe (2000) found a close correspondence between translucent growth bands on the cross-section of the hinge and yearly ^18O cycles. They conclude that the morphological features on hinge and growth bands on the cross-section are formed annually and can be used to determine accurately age and growth rate in this species. However, Surge et al. (2001) could not find that these morphologic features have seasonal significance in the C. virginica shells. Therefore, these concave ridges are not reliable independent proxies of seasonality. These studies were carried out with C. virginica shells; none was studied with nature C. gigas, which was widely distributed along the Pacific coastal area. C. gigas has been introduced from its native home to all over the world, ranging from North America to Australia and Europe; it has become an important commercial harvest in many of these places. Buried Holocene oyster shells of C. gigas were sampled from a huge buried oyster reef on the West of Bohai Sea, China. One of these shells was selected for high resolution micro-sampling and stable isotope analyses testing the assumption that C. gigas ligamental increments are annual in nature. We analyzed 236 consecutive samples from the shell to show that morphologic features both on hinge and cross-section are annual by comparing them to the ^18O profiles. We tested the assumption that the morphologic features of C.gigas are delineated by convex tops and concave bottoms on hinge and corresponding translucent growth bands on cross-section. The shell has 13.5 ligamental increments, based on 13.5 convex bands and 13 concave bottoms on hinge. Convex tops correspond to ^18O minima (summers), whereas concave bottoms correspond to ^18O maxima, which were formed during the low temperature of winter in the study area. We demonstrate that the ligamental increments of convex tops, concave bottoms and translucent growth bands in the studied C. gigas shell are suitable indicators of annual growth increments. The life spans, growth rates, and the timing of death can be determined from the ligament increments and isotope profiles of buried oyster shells.

A 100 au Wide Bipolar Rotating Shell Emanating from the HH 212 Protostellar Disk: A Disk Wind?

NASA Astrophysics Data System (ADS)

Lee, Chin-Fei; Li, Zhi-Yun; Codella, Claudio; Ho, Paul T. P.; Podio, Linda; Hirano, Naomi; Shang, Hsien; Turner, Neal J.; Zhang, Qizhou

2018-03-01

HH 212 is a Class 0 protostellar system found to host a “hamburger”-shaped dusty disk with a rotating disk atmosphere and a collimated SiO jet at a distance of ∼400 pc. Recently, a compact rotating outflow has been detected in SO and SO2 toward the center along the jet axis at ∼52 au (0.″13) resolution. Here we resolve the compact outflow into a small-scale wide-opening rotating outflow shell and a collimated jet, with the observations in the same S-bearing molecules at ∼16 au (0.″04) resolution. The collimated jet is aligned with the SiO jet, tracing the shock interactions in the jet. The wide-opening outflow shell is seen extending out from the inner disk around the SiO jet and has a width of ∼100 au. It is not only expanding away from the center, but also rotating around the jet axis. The specific angular momentum of the outflow shell is ∼40 au km s‑1. Simple modeling of the observed kinematics suggests that the rotating outflow shell can trace either a disk wind or disk material pushed away by an unseen wind from the inner disk or protostar. We also resolve the disk atmosphere in the same S-bearing molecules, confirming the Keplerian rotation there.

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.

Cortical inter-hemispheric circuits for multimodal vocal learning in songbirds.

PubMed

Paterson, Amy K; Bottjer, Sarah W

2017-10-15

Vocal learning in songbirds and humans is strongly influenced by social interactions based on sensory inputs from several modalities. Songbird vocal learning is mediated by cortico-basal ganglia circuits that include the SHELL region of lateral magnocellular nucleus of the anterior nidopallium (LMAN), but little is known concerning neural pathways that could integrate multimodal sensory information with SHELL circuitry. In addition, cortical pathways that mediate the precise coordination between hemispheres required for song production have been little studied. In order to identify candidate mechanisms for multimodal sensory integration and bilateral coordination for vocal learning in zebra finches, we investigated the anatomical organization of two regions that receive input from SHELL: the dorsal caudolateral nidopallium (dNCL SHELL ) and a region within the ventral arcopallium (Av). Anterograde and retrograde tracing experiments revealed a topographically organized inter-hemispheric circuit: SHELL and dNCL SHELL , as well as adjacent nidopallial areas, send axonal projections to ipsilateral Av; Av in turn projects to contralateral SHELL, dNCL SHELL , and regions of nidopallium adjacent to each. Av on each side also projects directly to contralateral Av. dNCL SHELL and Av each integrate inputs from ipsilateral SHELL with inputs from sensory regions in surrounding nidopallium, suggesting that they function to integrate multimodal sensory information with song-related responses within LMAN-SHELL during vocal learning. Av projections share this integrated information from the ipsilateral hemisphere with contralateral sensory and song-learning regions. Our results suggest that the inter-hemispheric pathway through Av may function to integrate multimodal sensory feedback with vocal-learning circuitry and coordinate bilateral vocal behavior. © 2017 Wiley Periodicals, Inc.

Graphitic carbon nitride nanosheet@metal-organic framework core-shell nanoparticles for photo-chemo combination therapy

NASA Astrophysics Data System (ADS)

Chen, Rui; Zhang, Jinfeng; Wang, Yu; Chen, Xianfeng; Zapien, J. Antonio; Lee, Chun-Sing

2015-10-01

Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX and the PDT effect of g-C3N4 nanosheets can lead to considerably enhanced efficacy. Furthermore, the red fluorescence of DOX and the blue fluorescence of g-C3N4 nanosheets provide the additional function of dual-color imaging for monitoring the drug release process.Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX and the PDT effect of g-C3N4 nanosheets can lead to considerably enhanced efficacy. Furthermore, the red fluorescence of DOX and the blue fluorescence of g-C3N4 nanosheets provide the additional function of dual-color imaging for monitoring the drug release process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04436g

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.

Utilizing stretch-tunable thermochromic elastomeric opal films as novel reversible switchable photonic materials.

PubMed

Schäfer, Christian G; Lederle, Christina; Zentel, Kristina; Stühn, Bernd; Gallei, Markus

2014-11-01

In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Micro CT Scanning to Assess Pteropod Shells in the Modern Ocean

NASA Astrophysics Data System (ADS)

Oakes, R. L.; Urbanski, J. M.; Bralower, T. J.

2016-02-01

Anthropogenic activities are causing fundamental changes to ocean chemistry. Calcareous plankton and nekton are predicted to be affected by these chemical changes, especially by ocean acidification. These groups are at the base of the marine food chain and therefore their demise will have a strong effect on the marine ecosystem as a whole. One challenge moving forward is to find a method to assess how chemical changes manifest themselves in plankton and nekton shells. Recent advancements in computed tomographic (CT) scanning technology allows for organisms to be imaged in three dimensions at micrometer resolution. CT data enables quantitative measurements of properties such as shell thickness, volume, and morphology. We apply this method to look at pteropods, nektonic molluscs which make their shells from the more soluble form of calcium carbonate, aragonite. Their shell mineralogy, and the fact that some groups live in polar and upwelling waters, place them at high risk for ocean acidification. We have scanned over 70 pteropods from 5 different locations globally. Analysis shows that there is a significant difference in pteropod shell thickness in different ocean basins with the thinnest shells being found off the coast of Washington. Changes in shell thickness may affect pteropod swimming efficiency, predation, and rate of sinking. Shell volume does not seem to vary with shell thickness suggesting that changes will impact pteropods at all ontogenetic stages. We are working towards a geometric morphometric analysis of these shells to see if the shape differs in areas with different ocean conditions. This initial set of CT scans of pteropods can be used as a baseline to which future changes can be compared. Furthermore, this technique has the potential to be easily transferred to other organisms as a method of assessing shell change in response to ocean acidification and associated factors.

Outlook and Challenges for Hydrogen Storage in Nanoporous Materials

DOE PAGES

Broom, D. P.; Webb, C. J.; Hurst, Katherine E.; ...

2016-02-16

Considerable progress has been made recently in the use of nanoporous materials for hydrogen storage. In our article, the current status of the field and future challenges are discussed, ranging from important open fundamental questions, such as the density and volume of the adsorbed phase and its relationship to overall storage capacity, to the development of new functional materials and complete storage system design. With regard to fundamentals, the use of neutron scattering to study adsorbed H 2, suitable adsorption isotherm equations, and the accurate computational modelling and simulation of H 2 adsorption are discussed. We cover new materials andmore » they include flexible metal–organic frameworks, core–shell materials, and porous organic cage compounds. The article concludes with a discussion of the experimental investigation of real adsorptive hydrogen storage tanks, the improvement in the thermal conductivity of storage beds, and new storage system concepts and designs.« less

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

Reflux condensation of pure vapors with and without a noncondensable gas inside plain and enhanced tubes

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

Abdelmessih, A.N.; Rabas, T.J.; Panchal, C.B.

1997-06-01

Estimates of the surface-area and vapor-release reductions are obtained when commercially available enhanced tubes (spirally ribbed) replace plain tubes in a reflux unit condensing pure organic vapors with different concentrations of a noncondensable gas. This investigation was undertaken because there are no existing data and/or prediction methods that are applicable for these shell-and-tube condensers commonly used in the process industries. To obtain these estimates, existing design methods published in the open literature were used. The major findings are that (1) surface-area reductions can almost approach the single-phase heat transfer enhancement level, and (2) vapor-release reductions can approach a factor ofmore » four. The important implication is that enhanced tubes appear to be very cost effective for addressing the recovery of volatile organic vapors (VOCs), and for a vast number of different reflux-condenser applications.« less

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

A Critical Appraisal of the Performance of Royal Dutch Shell as a Learning Organisation in the 1990s.

ERIC Educational Resources Information Center

Boyle, Emily

2002-01-01

Although Royal Dutch Shell had been identified as a "premiere learning organization," it had its worst results in 1998. Reasons included loss of commitment and community, leadership complacency, and inability to create a shared vision. Although management espoused learning organization principles, learning was not used for communal…

Polarimetry of nacre in iridescent shells

NASA Astrophysics Data System (ADS)

Metzler, R. A.; Burgess, C.; Regan, B.; Spano, S.; Galvez, E. J.

2014-09-01

We investigate the light transmitted or reflected from nacre (mother of pearl) taken from the iridescent shell of the bivalve Pinctad a fucata. These nacre surfaces have a rich structure, composed of aragonite crystals arranged as tablets or bricks, 5 μm wide and 400-500 nm thick, surrounded by 30nm thick organic mortar. The light reflected from these shell surfaces, or transmitted through thin polished layers, is rich in its polarization content, exhibiting a space dependent variation in the state of polarization with a high density of polarization singularities. Our goal is to use the polarization information to infer the structure of the biominerals and the role of the organic layer in determining the orientation of the crystals. In the experiments we send the light from a laser with a uniform state of polarization onto the shell, and analyze the light that is either transmitted or reflected, depending on the type of experiment, imaging it after its passage through polarization filters. We use the images from distinct filters to obtain the Stokes parameters, and hence the state of polarization, of each image point. We also construct the Mueller matrix for each imaged point, via 36 measurements. We do this for distinct physical and chemical treatments of the shell sample. Preliminary data shows that the organic layer may be responsible for organizing a multi-crystalline arrangement of aragonite tablets.

Regulation of Extracellular Matrix Synthesis by Shell Extracts from the Marine Bivalve Pecten maximus in Human Articular Chondrocytes- Application for Cartilage Engineering.

PubMed

Bouyoucef, Mouloud; Rakic, Rodolphe; Gómez-Leduc, Tangni; Latire, Thomas; Marin, Frédéric; Leclercq, Sylvain; Carreiras, Franck; Serpentini, Antoine; Lebel, Jean-Marc; Galéra, Philippe; Legendre, Florence

2018-04-07

The shells of the bivalve mollusks are organo-mineral structures predominantly composed of calcium carbonate, but also of a minor organic matrix, a mixture of proteins, glycoproteins, and polysaccharides. These proteins are involved in mineral deposition and, more generally, in the spatial organization of the shell crystallites in well-defined microstructures. In this work, we extracted different organic shell extracts (acid-soluble matrix, acid-insoluble matrix, water-soluble matrix, guanidine HCl/EDTA-extracted matrix, referred as ASM, AIM, WSM, and EDTAM, respectively) from the shell of the scallop Pecten maximus and studied their biological activities on human articular chondrocytes (HACs). We found that these extracts differentially modulate the biological activities of HACs, depending on the type of extraction and the concentration used. Furthermore, we showed that, unlike ASM and AIM, WSM promotes maintenance of the chondrocyte phenotype in monolayer culture. WSM increased the expression of chondrocyte-specific markers (aggrecan and type II collagen), without enhancing that of the main chondrocyte dedifferentiation marker (type I collagen). We also demonstrated that WSM could favor redifferentiation of chondrocyte in collagen sponge scaffold in hypoxia. Thus, this study suggests that the organic matrix of Pecten maximus, particularly WSM, may contain interesting molecules with chondrogenic effects. Our research emphasizes the potential use of WSM of Pecten maximus for cell therapy of cartilage.

Inorganic/organic nanocomposites: Reaching a high filler content without increasing viscosity using core-shell structured nanoparticles

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

Benhadjala, W., E-mail: warda.benhadjala@cea.fr; CEA, LETI, Minatec Campus, 38000 Grenoble; Gravoueille, M.

2015-11-23

Extensive research is being conducted on the development of inorganic/organic nanocomposites for a wide variety of applications in microelectronics, biotechnologies, photonics, adhesives, or optical coatings. High filler contents are usually required to fully optimize the nanocomposites properties. However, numerous studies demonstrated that traditional composite viscosity increases with increasing the filler concentration reducing therefore significantly the material processability. In this work, we synthesized inorganic/organic core-shell nanocomposites with different shell thicknesses. By reducing the shell thickness while maintaining a constant core size, the nanoparticle molecular mass decreases but the nanocomposite filler fraction is correlatively increased. We performed viscosity measurements, which clearly highlightedmore » that intrinsic viscosity of hybrid nanoparticles decreases as the molecular mass decreases, and thus, as the filler fraction increases, as opposed to Einstein predictions about the viscosity of traditional inorganic/polymer two-phase mixtures. This exceptional behavior, modeled by Mark-Houwink-Sakurada equation, proves to be a significant breakthrough for the development of industrializable nanocomposites with high filler contents.« less

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.

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

Method of fabricating nested shells and resulting product

DOEpatents

Henderson, Timothy M.; Kool, Lawrence B.

1982-01-01

A multiple shell structure and a method of manufacturing such structure wherein a hollow glass microsphere is surface treated in an organosilane solution so as to render the shell outer surface hydrophobic. The surface treated glass shell is then suspended in the oil phase of an oil-aqueous phase dispersion. The oil phase includes an organic film-forming monomer, a polymerization initiator and a blowing agent. A polymeric film forms at each phase boundary of the dispersion and is then expanded in a blowing operation so as to form an outer homogeneously integral monocellular substantially spherical thermoplastic shell encapsulating an inner glass shell of lesser diameter.

MOF-derived hierarchical double-shelled NiO/ZnO hollow spheres for high-performance supercapacitors.

PubMed

Li, Guo-Chang; Liu, Peng-Fei; Liu, Rui; Liu, Minmin; Tao, Kai; Zhu, Shuai-Ru; Wu, Meng-Ke; Yi, Fei-Yan; Han, Lei

2016-09-14

Nanorods-composed yolk-shell bimetallic-organic frameworks microspheres are successfully synthesized by a one-step solvothermal method in the absence of any template or surfactant. Furthermore, hierarchical double-shelled NiO/ZnO hollow spheres are obtained by calcination of the bimetallic organic frameworks in air. The NiO/ZnO hollow spheres, as supercapacitor electrodes, exhibit high capacitance of 497 F g(-1) at the current density of 1.3 A g(-1) and present a superior cycling stability. The superior electrochemical performance is believed to come from the unique double-shelled NiO/ZnO hollow structures, which offer free space to accommodate the volume change during the ion insertion and desertion processes, as well as provide rich electroactive sites for the electrochemical reactions.

Limacina retroversa's response to combined effects of ocean acidification and sea water freshening

NASA Astrophysics Data System (ADS)

Manno, C.; Morata, N.; Primicerio, R.

2012-11-01

Anthropogenic carbon dioxide emissions induce ocean acidification, thereby reducing carbonate ion concentration, which may affect the ability of calcifying organisms to build shells. Pteropods, the main planktonic producers of aragonite in the worlds' oceans, may be particularly vulnerable to changes in sea water chemistry. The negative effects are expected to be most severe at high-latitudes, where natural carbonate ion concentrations are low. In this study we investigated the combined effects of ocean acidification and freshening on Limacina retroversa, the dominant pteropod in sub polar areas. Living L. retroversa, collected in Northern Norwegian Sea, were exposed to four different pH values ranging from the pre-industrial level to the forecasted end of century ocean acidification scenario. Since over the past half-century the Norwegian Sea has experienced a progressive freshening with time, each pH level was combined with a salinity gradient in two factorial, randomized experiments investigating shell degradation, swimming behavior and survival. In addition, to investigate shell degradation without any physiologic influence, one perturbation experiments using only shells of dead pteropods was performed. Lower pH reduced shell mass whereas shell dissolution increased with pCO2. Interestingly, shells of dead organisms had a higher degree of dissolution than shells of living individuals. Mortality of Limacina retroversa was strongly affected only when both pH and salinity reduced simultaneously. The combined effects of lower salinity and lower pH also affected negatively the ability of pteropods to swim upwards. Results suggest that the energy cost of maintaining ion balance and avoiding sinking (in low salinity scenario) combined with the extra energy cost necessary to counteract shell dissolution (in high pCO2 scenario), exceed the available energy budget of this organism causing the pteropods to change swimming behavior and begin to collapse. Since L. retroversa play an important role in the transport of carbonates to the deep oceans these findings have significant implications for the mechanisms influencing the inorganic carbon cycle in the sub-polar area.

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

A universal cooperative assembly-directed method for coating of mesoporous TiO2 nanoshells with enhanced lithium storage properties

PubMed Central

Guan, Bu Yuan; Yu, Le; Li, Ju; Lou, Xiong Wen (David)

2016-01-01

TiO2 is exceptionally useful, but it remains a great challenge to develop a universal method to coat TiO2 nanoshells on different functional materials. We report a one-pot, low-temperature, and facile method that can rapidly form mesoporous TiO2 shells on various inorganic, organic, and inorganic-organic composite materials, including silica-based, metal, metal oxide, organic polymer, carbon-based, and metal-organic framework nanomaterials via a cooperative assembly-directed strategy. In constructing hollow, core-shell, and yolk-shell geometries, both amorphous and crystalline TiO2 nanoshells are demonstrated with excellent control. When used as electrode materials for lithium ion batteries, these crystalline TiO2 nanoshells composed of very small nanocrystals exhibit remarkably long-term cycling stability over 1000 cycles. The electrochemical properties demonstrate that these TiO2 nanoshells are promising anode materials. PMID:26973879

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.

76 FR 59763 - Self-Regulatory Organizations; NYSE Amex LLC; Notice of Designation of a Longer Period for...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-27

... Requirements for Companies Applying To List After Consummation of a ``Reverse Merger'' With a Shell Company... shell company. The proposed rule change was published for comment in the Federal Register on August 10... companies applying to list after consummation of a ``reverse merger'' with a shell company, and to consider...

Endoliths in Lithophaga lithophaga shells--Variation in intensity of infestation and species occurrence.

PubMed

Peharda, Melita; Calcinai, Barbara; Puljas, Sanja; Golubić, Stjepko; Arapov, Jasna; Thébault, Julien

2015-07-01

Pronounced differences with respect to the extent of infestation and the degree of Lithophaga lithophaga shell damage inflicted by euendolithic taxa at two sites in the Adriatic Sea representing different productivity conditions, are described. Shells collected from the eastern part of Kaštela Bay, which is characterized by higher primary productivity, have significantly more shell damage then the shell collected from a site on the outer coast of the island of Čiovo exposed to the oligotrophic Adriatic Sea. The presence of endoliths and their perforations were detected in different layers of the shell, including solidly mineralized parts of the skeleton and within the organic lamellae incorporated into the shell. Phototrophic endoliths were not observed in the specimens. The most serious damage to L. lithophaga shells was the boring clionaid sponge Pione vastifica, which was more common in shells collected from Kaštela. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Theoretical investigation of gas-surface interactions

NASA Technical Reports Server (NTRS)

Dyall, Kenneth G.

1992-01-01

The investigation into the appearance of intruder states from the negative continuum when some of the two-electron integrals were omitted was completed. The work shows that, provided all integrals involving core contracted functions in an atomic general contraction are included, or that the core functions are radially localized, meaningful results are obtained and intruder states do not appear. In the area of program development, the Dirac-Hartree-Fock (DHF) program for closed-shell polyatomic molecules was extended to permit Kramers-restricted open-shell DHF calculations with one electron in an open shell or one hole in a closed shell, or state-averaged DHF calculations over several particle or hole doublet states. One application of the open-shell code was to the KO molecule. Another major area of program development is the transformation of integrals from the scalar basis in which they are generated to the 2-spinor basis employed in parts of the DHF program, and hence to supermatrix form. Particularly concerning the omission of small component integrals, and with increase in availability of disk space, it is now possible to consider transforming the integrals. The use of ordered integrals, either in the scalar basis or in the 2-spinor basis, would considerably speed up the construction of the Fock matrix, and even more so if supermatrices were constructed. A considerable amount of effort was spent on analyzing the integral ordering and tranformation for the DHF program. The work of assessing the reliability of the relativistic effective core potentials (RECPs) was continued with calculation of the group IV monoxides. The perturbation of the metal atom provided by oxygen is expected to be larger than that provided by hydrogen and thus provide a better test of the qualification of the RECPs. Calculations on some platinum hydrides were carried out at nonrelativistic (NR), perturbation theory (PT) and DHF levels. Reprints of four papers describing this work are included.

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.

Review on the preparation and modified technologies of microencapsulated red phosphorus

NASA Astrophysics Data System (ADS)

Cheng, Chen; Du, Shiguo; Yan, Jun

2017-10-01

Coated by a compact shell structure, pristine red phosphorus transforms into microcapsule red phosphorus (MCRP) with lower PH3 emission and improved compatibility with polymer matrix. Diverse kinds of microcapsule red phosphorus are classified by shell material, i.e.organic shell material MCRP, inorganic shell material MCRP and composite shell material MCRP. Furthermore, the modified technology to make up deficiencies of MCRP is also introduced in the lecture. Aiming at the existing microencapsulation craft, a more harmless and high-efficiency process should be presented, and ultrafine MCRP is also urgent to be prepared.

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

Modeling the carbon isotope composition of bivalve shells (Invited)

NASA Astrophysics Data System (ADS)

Romanek, C.

2010-12-01

The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., <10%) in shells from aquatic organism and high (>90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions, equilibrium carbon isotope fractionation relations dictate that shell carbonate should be preferentially enriched in C-13 by 3 to 5 per mill (from 30° to 0°C) compared to EPF at a pH of 7.5. Anomalous positive excursions are rarely, if ever, observed in shell carbonate and they have yet to be associated with growth cessation markers in bivalves. The most likely explanation for the lack of anomalous positive values is that the percentage of metabolic carbon increases in EPF when bivalves experience stressful condition. This influx of metabolic carbon is balanced to a measureable extent by the enhanced fractionation of carbon isotopes during shell deposition from EPF at relatively low pH. These two processes may be combined in a quantitative model to extract a historical record of metabolic activity from the carbon isotope profiles of bivalve shells.

High-resolution nitrogen stable isotope sclerochronology of bivalve shell carbonate-bound organics

NASA Astrophysics Data System (ADS)

Gillikin, David P.; Lorrain, Anne; Jolivet, Aurélie; Kelemen, Zita; Chauvaud, Laurent; Bouillon, Steven

2017-03-01

Nitrogen stable isotope ratios (δ15N) of organic material have successfully been used to track food-web dynamics, nitrogen baselines, pollution, and nitrogen cycling. Extending the δ15N record back in time has not been straightforward due to a lack of suitable substrates in which δ15N records are faithfully preserved, thus sparking interest in utilizing skeletal carbonate-bound organic matter (CBOM) in mollusks, corals, and foraminifera. Here we test if calcite Pecten maximus shells from the Bay of Brest and the French continental shelf can be used as an archive of δ15N values over a large environmental gradient and at a high temporal resolution (approximately weekly). Bulk CBOM δ15N values from the growing tip of shells collected over a large nitrogen isotope gradient were strongly correlated with adductor muscle tissue δ15N values (R2 = 0.99, n = 6, p < 0.0001). We were able to achieve weekly resolution (on average) over the growing season from sclerochronological profiles of three shells, which showed large seasonal variations up to 3.4‰. However, there were also large inter-specimen differences (up to 2.5‰) between shells growing at the same time and location. Generally, high-resolution shell δ15N values follow soft-tissue δ15N values, but soft-tissues integrate more time, hence soft-tissue data are more time-averaged and smoothed. Museum-archived shells from the 1950s, 1965, and 1970s do not show a large difference in δ15N values through time despite expected increasing N loading to the Bay over this time, which could be due to anthropogenic N sources with contrasting values. Compiling shell CBOM δ15N data from several studies suggests that the offset between soft-tissue and shell δ15N values (Δtissue-shell) differs between calcite and aragonite shells. We hypothesize that this difference is caused by differences in amino acids used in constructing the different minerals, which should be specific to the CaCO3 polymorph being constructed. Future work should use compound specific isotope analyses (CSIA) to test this hypothesis, and to determine whether certain amino acids could specifically track N sources or possibly identify amino acids that are more resistant to diagenesis in fossil shells. In conclusion, bivalve shell CBOM δ15N values can be used in a similar manner to soft-tissue δ15N values, and can track various biogeochemical events at a very high-resolution.

Characteristics and aging of traffic-derived particles in a highway tunnel at a coastal city in southern China.

PubMed

Hou, Cong; Shao, Longyi; Hu, Wei; Zhang, Daizhou; Zhao, Chengmei; Xing, Jiaoping; Huang, Xiaofeng; Hu, Min

2018-04-01

Road traffic is one of the major sources of particulate matters in the atmosphere. Tunnels provide a semi-closed place to measure traffic-derived particles before the particles were photo-chemically modified in the open air. In this study, aerosol particles were collected in a tunnel, and an urban site for comparison at a coastal city in south China. The particles were analyzed by using a transmission electron microscope coupled with an energy-dispersive X-ray spectrometry. There were four groups of particles according to sources: tailpipe-emitted particles, wear debris, road dust, and secondary particles. Tailpipe-emitted particles included soot, organic, and a part of sulfate and metal particles. Wear debris were characterized by their distinct metal components. Road dust was composed of mineral particles and fly ash. Secondary particles were some sulfate particles and mixture particles. Sulfate particles were further divided into two subtypes: with and without organic coating. Sulfate particles with organic coating accounted for 56.2% of total sulfate particles in the tunnel, while the percentage was 36.9% at the urban site, indicating that sulfate particles were more easily coated by organics in the tunnel than the urban site. However, the aging degree of sulfate particles in the tunnel was weaker than that at the urban site, which was attributed to the absence of photochemical reactions in the tunnel environment. Some mixture particles had a core-shell structure (C-S particles). The composition and morphologies of the cores of the C-S particles were similar to those of mineral, metal, and mixture particles. The shells of the C-S particles were mainly composed of organics. The C-S particles were more aged than the sulfate particles with coating in the tunnel environment, suggesting that mineral and metal components could efficiently enhance particle aging in the absence of photochemical reactions. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Energy-Cascaded Upconversion in an Organic Dye-Sensitized Core/Shell Fluoride Nanocrystal.

PubMed

Chen, Guanying; Damasco, Jossana; Qiu, Hailong; Shao, Wei; Ohulchanskyy, Tymish Y; Valiev, Rashid R; Wu, Xiang; Han, Gang; Wang, Yan; Yang, Chunhui; Ågren, Hans; Prasad, Paras N

2015-11-11

Lanthanide-doped upconversion nanoparticles hold promises for bioimaging, solar cells, and volumetric displays. However, their emission brightness and excitation wavelength range are limited by the weak and narrowband absorption of lanthanide ions. Here, we introduce a concept of multistep cascade energy transfer, from broadly infrared-harvesting organic dyes to sensitizer ions in the shell of an epitaxially designed core/shell inorganic nanostructure, with a sequential nonradiative energy transfer to upconverting ion pairs in the core. We show that this concept, when implemented in a core-shell architecture with suppressed surface-related luminescence quenching, yields multiphoton (three-, four-, and five-photon) upconversion quantum efficiency as high as 19% (upconversion energy conversion efficiency of 9.3%, upconversion quantum yield of 4.8%), which is about ~100 times higher than typically reported efficiency of upconversion at 800 nm in lanthanide-based nanostructures, along with a broad spectral range (over 150 nm) of infrared excitation and a large absorption cross-section of 1.47 × 10(-14) cm(2) per single nanoparticle. These features enable unprecedented three-photon upconversion (visible by naked eye as blue light) of an incoherent infrared light excitation with a power density comparable to that of solar irradiation at the Earth surface, having implications for broad applications of these organic-inorganic core/shell nanostructures with energy-cascaded upconversion.

Bioerosion of gastropod shells: with emphasis on effects of coralline algal cover and shell microstructure

NASA Astrophysics Data System (ADS)

Smyth, Miriam J.

1989-12-01

Organisms boring into fifty nine species of gastropod shells on reefs around Guam were the bryozoan Penetrantia clionoides; the acrothoracian barnacles Cryptophialus coronorphorus, Cryptophialus zulloi and Lithoglyptis mitis; the foraminifer Cymbaloporella tabellaeformis, the polydorid Polydora sp. and seven species of clionid sponge. Evidence that crustose coralline algae interfere with settlement of larvae of acrothoracian barnacles, clionid sponges, and boring polychaetes came from two sources: (1) low intensity of boring in limpet shells, a potentially penetrable substrate that remains largely free of borings by virtue of becoming fully covered with coralline algae at a young age and (2) the extremely low levels of boring in the algal ridge, a massive area of carbonate almost entirely covered by a layer of living crustose corallines. There was a strong negative correlation between microstructural hardness and infestation by acrothoracian barnacles and no correlation in the case of the other borers. It is suggested that this points to a mechanical rather than a chemical method of boring by the barnacles. The periostracum, a layer of organic material reputedly a natural inhibitor of boring organisms, was bored by acrothoracican barnacles and by the bryozoan. The intensity of acrothoracican borings is shown to have no correlation with the length of the gastropod 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.

Study of clusters using negative ion photodetachment spectroscopy

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

Zhao, Yuexing

1995-12-01

The weak van der Waals interaction between an open-shell halogen atom and a closed-shell atom or molecule has been investigated using zero electron kinetic energy (ZEKE) spectroscopy. This technique is also applied to study the low-lying electronic states in GaAs and GaAs -. In addition, the spectroscopy and electron detachment dynamics of several small carbon cluster anions are studied using resonant multiphoton detachment spectroscopy.

An aqueous, organic dye derivatized SnO 2 /TiO 2 core/shell photoanode

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

Wee, Kyung-Ryang; Sherman, Benjamin D.; Brennaman, M. Kyle

2016-01-01

Visible light driven water splitting in a dye-sensitized photoelectrochemical cell (DSPEC) based on a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic dye (P–A–π–D) is described with the dye anchored to an FTO|SnO 2/TiO 2core/shell photoanode in a pH 7 phosphate buffer solution.

Composted oyster shell as lime fertilizer is more effective than fresh oyster shell.

PubMed

Lee, Young Han; Islam, Shah Md Asraful; Hong, Sun Joo; Cho, Kye Man; Math, Renukaradhya K; Heo, Jae Young; Kim, Hoon; Yun, Han Dae

2010-01-01

Physio-chemical changes in oyster shell were examined, and fresh and composted oyster shell meals were compared as lime fertilizers in soybean cultivation. Structural changes in oyster shell were observed by AFM and FE-SEM. We found that grains of the oyster shell surface became smoother and smaller over time. FT-IR analysis indicated the degradation of a chitin-like compound of oyster shell. In chemical analysis, pH (12.3+/-0.24), electrical conductivity (4.1+/-0.24 dS m(-1)), and alkaline powder (53.3+/-1.12%) were highest in commercial lime. Besides, pH was higher in composted oyster shell meal (9.9+/-0.53) than in fresh oyster shell meal (8.4+/-0.32). The highest organic matter (1.1+/-0.08%), NaCl (0.54+/-0.03%), and moisture (15.1+/-1.95%) contents were found in fresh oyster shell meal. A significant higher yield of soybean (1.33 t ha(-1)) was obtained by applying composted oyster shell meal (a 21% higher yield than with fresh oyster shell meal). Thus composting of oyster shell increases the utility of oyster shell as a liming material for crop cultivation.

Mathematical modelling of fluid transport and its regulation at multiple scales.

PubMed

Chara, Osvaldo; Brusch, Lutz

2015-04-01

Living matter equals water, to a first approximation, and water transport across barriers such as membranes and epithelia is vital. Water serves two competing functions. On the one hand, it is the fundamental solvent enabling random mobility of solutes and therefore biochemical reactions and intracellular signal propagation. Homeostasis of the intracellular water volume is required such that messenger concentration encodes the stimulus and not inverse volume fluctuations. On the other hand, water flow is needed for transport of solutes to and away from cells in a directed manner, threatening volume homeostasis and signal transduction fidelity of cells. Feedback regulation of fluid transport reconciles these competing objectives. The regulatory mechanisms often span across multiple spatial scales from cellular interactions up to the architecture of organs. Open questions relate to the dependency of water fluxes and steady state volumes on control parameters and stimuli. We here review selected mathematical models of feedback regulation of fluid transport at the cell scale and identify a general "core-shell" structure of such models. We propose that fluid transport models at other spatial scales can be constructed in a generalised core-shell framework, in which the core accounts for the biophysical effects of fluid transport whilst the shell reflects the regulatory mechanisms. We demonstrate the applicability of this framework for tissue lumen growth and suggest future experiments in zebrafish to test lumen size regulation mechanisms. Copyright © 2015 Elsevier Ireland Ltd. 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).

Position-controlled MOVPE growth and electro-optical characterization of core-shell InGaN/GaN microrod LEDs

NASA Astrophysics Data System (ADS)

Schimpke, Tilman; Lugauer, H.-J.; Avramescu, A.; Varghese, T.; Koller, A.; Hartmann, J.; Ledig, J.; Waag, A.; Strassburg, M.

2016-03-01

Today's InGaN-based white LEDs still suffer from a significant efficiency reduction at elevated current densities, the so-called "Droop". Core-shell microrods, with quantum wells (QWs) covering their entire surface, enable a tremendous increase in active area scaling with the rod's aspect ratio. Enlarging the active area on a given footprint area is a viable and cost effective route to mitigate the droop by effectively reducing the local current density. Microrods were grown in a large volume metal-organic vapor phase epitaxy (MOVPE) reactor on GaN-on-sapphire substrates with a thin, patterned SiO2 mask for position control. Out of the mask openings, pencil-shaped n-doped GaN microrod cores were grown under conditions favoring 3D growth. In a second growth step, these cores are covered with a shell containing a quantum well and a p-n junction to form LED structures. The emission from the QWs on the different facets was studied using resonant temperature-dependent photoluminescence (PL) and cathodoluminescence (CL) measurements. The crystal quality of the structures was investigated by transmission electron microscopy (TEM) showing the absence of extended defects like threading dislocations in the 3D core. In order to fabricate LED chips, dedicated processes were developed to accommodate for the special requirements of the 3D geometry. The electrical and optical properties of ensembles of tens of thousands microrods connected in parallel are discussed.

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.

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.

Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

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

O'Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.

2015-04-21

Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed thatmore » both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.« less

What determines sclerobiont colonization on marine mollusk shells?

PubMed

Ochi Agostini, Vanessa; Ritter, Matias do Nascimento; José Macedo, Alexandre; Muxagata, Erik; Erthal, Fernando

2017-01-01

Empty mollusk shells may act as colonization surfaces for sclerobionts depending on the physical, chemical, and biological attributes of the shells. However, the main factors that can affect the establishment of an organism on hard substrates and the colonization patterns on modern and time-averaged shells remain unclear. Using experimental and field approaches, we compared sclerobiont (i.e., bacteria and invertebrate) colonization patterns on the exposed shells (internal and external sides) of three bivalve species (Anadara brasiliana, Mactra isabelleana, and Amarilladesma mactroides) with different external shell textures. In addition, we evaluated the influence of the host characteristics (mode of life, body size, color alteration, external and internal ornamentation and mineralogy) of sclerobionts on dead mollusk shells (bivalve and gastropod) collected from the Southern Brazilian coast. Finally, we compared field observations with experiments to evaluate how the biological signs of the present-day invertebrate settlements are preserved in molluscan death assemblages (incipient fossil record) in a subtropical shallow coastal setting. The results enhance our understanding of sclerobiont colonization over modern and paleoecology perspectives. The data suggest that sclerobiont settlement is enhanced by (i) high(er) biofilm bacteria density, which is more attracted to surfaces with high ornamentation; (ii) heterogeneous internal and external shell surface; (iii) shallow infaunal or attached epifaunal life modes; (iv) colorful or post-mortem oxidized shell surfaces; (v) shell size (<50 mm2 or >1,351 mm2); and (vi) calcitic mineralogy. Although the biofilm bacteria density, shell size, and texture are considered the most important factors, the effects of other covarying attributes should also be considered. We observed a similar pattern of sclerobiont colonization frequency over modern and paleoecology perspectives, with an increase of invertebrates occurring on textured bivalve shells. This study demonstrates how bacterial biofilms may influence sclerobiont colonization on biological hosts (mollusks), and shows how ecological relationships in marine organisms may be relevant for interpreting the fossil record of sclerobionts.

What determines sclerobiont colonization on marine mollusk shells?

PubMed Central

José Macedo, Alexandre; Muxagata, Erik; Erthal, Fernando

2017-01-01

Empty mollusk shells may act as colonization surfaces for sclerobionts depending on the physical, chemical, and biological attributes of the shells. However, the main factors that can affect the establishment of an organism on hard substrates and the colonization patterns on modern and time-averaged shells remain unclear. Using experimental and field approaches, we compared sclerobiont (i.e., bacteria and invertebrate) colonization patterns on the exposed shells (internal and external sides) of three bivalve species (Anadara brasiliana, Mactra isabelleana, and Amarilladesma mactroides) with different external shell textures. In addition, we evaluated the influence of the host characteristics (mode of life, body size, color alteration, external and internal ornamentation and mineralogy) of sclerobionts on dead mollusk shells (bivalve and gastropod) collected from the Southern Brazilian coast. Finally, we compared field observations with experiments to evaluate how the biological signs of the present-day invertebrate settlements are preserved in molluscan death assemblages (incipient fossil record) in a subtropical shallow coastal setting. The results enhance our understanding of sclerobiont colonization over modern and paleoecology perspectives. The data suggest that sclerobiont settlement is enhanced by (i) high(er) biofilm bacteria density, which is more attracted to surfaces with high ornamentation; (ii) heterogeneous internal and external shell surface; (iii) shallow infaunal or attached epifaunal life modes; (iv) colorful or post-mortem oxidized shell surfaces; (v) shell size (<50 mm2 or >1,351 mm2); and (vi) calcitic mineralogy. Although the biofilm bacteria density, shell size, and texture are considered the most important factors, the effects of other covarying attributes should also be considered. We observed a similar pattern of sclerobiont colonization frequency over modern and paleoecology perspectives, with an increase of invertebrates occurring on textured bivalve shells. This study demonstrates how bacterial biofilms may influence sclerobiont colonization on biological hosts (mollusks), and shows how ecological relationships in marine organisms may be relevant for interpreting the fossil record of sclerobionts. PMID:28902894

Biocatalytic CO2 sequestration based on shell regeneration

NASA Astrophysics Data System (ADS)

Lee, S.

2012-04-01

Carbon dioxide, CO2, is one of the green gases, being uniformly distributed over the earth's surface. Recently, a variety of methods exists or has been proposed for pre- or post-emission capture and sequestration of CO2. However, CCS (carbon capture & storage) do not quarntee permanent treatment of CO2 and could ingenerate environment risks. Some organisms convert CO2 into exoskeleton (e.g., mollusks) or energy sources (e.g., plants) during metabolism under atmospheric conditions. One of representative biomaterials in ocean is bivalve shell to be composed of CaCO3. Calcium carbonate is not only abundant material in the world but also thermodynamically stable mineral in the capture of CO2. Bivalve has produced CaCO3 under seawater condition, in other word, near atmospheric conditions (1 atm. and around 20-25 oC). At the inorganic point, the synthesis of CaCO3 is as followed. Ca2+ + CO32- -> CaCO3 The bivalve shell plays an important role to protect bivalve's internal organs from prodetor. What will be happened if the shell is damaged and a hole is made? Bivalve must cover the hole to prevent the oxidation of internal organs as fast as possible. From in vitro crystallization test of a notched shell, rapid CaCO3 production was identified at the damaged area. The biocatalyst related to shell regeneration was purified and named as SPSR (Soluble Protein related to Shell Regeneration) that is obtained from the oyster, Crassostrea gigas. And in vitro CaCO3 crystallization test was used to calculate the crystal growth rate of SPSR on CaCO3 crystallization. The characteristics of SPRR are discussed at the point of CO2 hydration and rapid CaCO3 synthesis. To develop the bioinspired process based on shell regeneration concept, the analysis of protein structure has been studied and the immobilization has been carried out for easy recovery of SPSR.

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

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.

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

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.

Organic filler from golden apple snails shells to improve the silicone rubber insulator properties

NASA Astrophysics Data System (ADS)

Tepsila, Sujirat; Suksri, Amnart

2018-02-01

This paper investigates the effect of an addition of filler compound using golden apple snail shell as an organic filler to the silicone rubber insulator. The filler obtained from golden apple snail shell is found mostly contained calcium carbonate. The organic calcium carbonate (CaCO3) with particle size of 45, 75, 100 and 300 micron were prepared. Sample of silicone rubber that were filled with fillers were tested under ASTM D638-02a type standard for mechanical test. Also, electrical test such as I-V characteristics (ASTM D257-07) and dry arc test according to ASTM D495-14 have been performed. The results revealed that using larger particle size of organic filler obtained from the golden apple snail shell resulted to higher value of dielectric constant as well as higher dielectric strength. Also, the filler helps slow down the tracking activity at an insulator surface due to its crystals of calcium carbonate. However, when using excessive amount of filler, the sample will have a drawbacks in mechanical properties. By using agriculture waste as a filler compound, one can reduced the usage of commercial CaCO3 as an inorganic materials and to lower the investment cost to a final silicone rubber product.

Early post-mortem formation of carbonate concretions around tusk-shells over week-month timescales

NASA Astrophysics Data System (ADS)

Yoshida, Hidekazu; Ujihara, Atsushi; Minami, Masayo; Asahara, Yoshihiro; Katsuta, Nagayoshi; Yamamoto, Koshi; Sirono, Sin-Iti; Maruyama, Ippei; Nishimoto, Shoji; Metcalfe, Richard

2015-09-01

Carbonate concretions occur in sedimentary rocks of widely varying geological ages throughout the world. Many of these concretions are isolated spheres, centered on fossils. The formation of such concretions has been variously explained by diffusion of inorganic carbon and organic matter in buried marine sediments. However, details of the syn-depositional chemical processes by which the isolated spherical shape developed and the associated carbon sources are little known. Here we present evidence that spherical carbonate concretions (diameters φ : 14 ~ 37 mm) around tusk-shells (Fissidentalium spp.) were formed within weeks or months following death of the organism by the seepage of fatty acid from decaying soft body tissues. Characteristic concentrations of carbonate around the mouth of a tusk-shell reveal very rapid formation during the decay of organic matter from the tusk-shell. Available observations and geochemical evidence have enabled us to construct a ‘Diffusion-growth rate cross-plot’ that can be used to estimate the growth rate of all kinds of isolated spherical carbonate concretions identified in marine formations. Results shown here suggest that isolated spherical concretions that are not associated with fossils might also be formed from carbon sourced in the decaying soft body tissues of non-skeletal organisms with otherwise low preservation potential.

Single molecule conductivity: the role of junction-orbital degeneracy in the artificially high currents predicted by ab initio approaches.

PubMed

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

2004-10-08

A priori evaluations, using Hartree-Fock self-consistent-field (SCF) theory or density-functional theory (DFT), of the current passing between two electrodes through a single bridging molecule result in predicted conductivities that may be up to one to two orders of magnitude larger than observed ones. We demonstrate that this is, in part, often due to the improper application of the computational methods. Conductivity is shown to arise from tunneling between junction states of the electrodes through the molecule; these states are inherently either quasi two-fold or four-fold degenerate and always comprise the (highest occupied molecular orbital) HOMO band at the Fermi energy of the system. Frequently, in previous cluster based molecular conduction calculations, closed-shell SCF or Kohn-Sham DFT methods have been applied to systems that we demonstrate to be intrinsically open shell in nature. Such calculations are shown to induce artificial HOMO-LUMO (LUMO-lowest unoccupied molecular orbital) band splittings that Landauer-based formalisms for steady-state conduction interpret as arising from extremely rapid through-molecule tunneling at the Fermi energy, hence, overestimating the low-voltage conductivity. It is demonstrated that these shortcomings can be eliminated, dramatically reducing calculated current magnitudes, through the alternate use of electronic-structure calculations based on the spin-restricted open-shell formalism and related multiconfigurational SCF of DFT approaches. Further, we demonstrate that most anomalies arising in DFT implementations arise through the use of hybrid density functionals such as B3LYP. While the enhanced band-gap properties of these functionals have made them the defacto standard in molecular conductivity calculations, we demonstrate that it also makes them particularly susceptible to open-shell anomalies.

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

Organosolv extraction of lignin from hydrolyzed almond shells and application of the delta-value theory.

PubMed

Quesada-Medina, Joaquín; López-Cremades, Francisco Javier; Olivares-Carrillo, Pilar

2010-11-01

The solubility of lignin from hydrolyzed almond (Prunus amygdalus) shells in different acetone, ethanol and dioxane-water mixtures and conditions (extraction time and temperature) was studied. The concept of the solubility parameter (delta-value) was applied to explain the effect of organic solvent concentration on lignin solubility. The organic solvent-water mixture that led to the highest lignin extraction was composed of a 75% vol. of organic solvent for all the solvent series investigated (acetone, ethanol and dioxane). Moreover, the best lignin extraction conditions were a temperature of 210 degrees C and an extraction time of 40 min for the acetone and ethanol series, and 25 min for the dioxane series. The delta-value of the hydrolyzed almond shell lignin [14.60 (cal/cm(3))(1/2)] and that of the organic solvent-water mixtures was calculated. The experimental delignification capacity of the aqueous organic solvents clearly reflected the proximity of their delta-value to that of lignin. The hydrogen-bonding capacity of the solvent-water mixtures was also taken into account. Copyright 2010 Elsevier Ltd. All rights reserved.

A facile in situ self-assembly strategy for large-scale fabrication of CHS@MOF yolk/shell structure and its catalytic application in a flow system.

PubMed

Gao, Hongyi; Luan, Yi; Chaikittikul, Kullapat; Dong, Wenjun; Li, Jie; Zhang, Xiaowei; Jia, Dandan; Yang, Mu; Wang, Ge

2015-03-04

A hierarchical yolk/shell copper hydroxysulfates@MOF (CHS@MOF, where MOF = metal-organic frameworks) structure was fabricated from a homogeneous yolk/shell CHS template composed of an active shell and a stabilized core via a facile self-template strategy at room temperature. The active shell of the template served as the source of metal ion and was in situ transformed into a well-defined MOF crystal shell, and the relatively stabilized core retained its own nature during the formation of the MOF shell. The strategy of in situ transformation of CHS shell to MOF shell avoided the self-nucleation of MOF in the solution and complex multistep procedures. Furthermore, a flow reaction system using CHS@MOF as self-supported stationary-phase catalyst was developed, which demonstrated excellent catalytic performance for aldehyde acetalization with ethanol, and high yields and selectivities were achieved under mild conditions.

Elevated extracellular pH during early shell formation in the blue mussel Mytilus edulis

NASA Astrophysics Data System (ADS)

Ramesh, K.; Melzner, F.; Himmerkus, N.; Hu, M.; Bleich, M.

2016-02-01

Marine calcifiers are amongst the most vulnerable organisms to ocean acidification (OA). However, limited studies investigate the mechanisms underlying their hindered performance under OA stress. Working with larval stages of the blue mussel, Mytilus edulis, we use microsensors to study the pH and calcium conditions necessary for shell deposition. Using 45-48 hour, D-veliger stages, we discover alkaline conditions with respect to ambient seawater pH by 0.28 pH units and higher calcium concentrations (by 0.54mM) in the extra pallial space beneath the growing shell that likely promotes the rapid synthesis of the first shell. We further use enzyme assays in combination with immuno-stainings of sodium-potassium ATPase (NKA) and proton ATPase (VHA) to provide information on the major ion regulatory pathways that enable transport of calcium carbonate required for shell formation and pH homeostasis. We also use the juvenile stages of M. edulis to understand how extracellular pH regulation close to the shell formation site will be influenced by OA stress. This allows us to describe the pH dependency of early shell formation and to begin to develop a model of the ion regulatory network that facilitates biomineralisation in the organism. The results are discussed in the context of environmental change and consequences for mollusc developmental success.

Problems in understanding the structure and assembly of viruses

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

King, J.

1997-12-01

Though viruses infect the cells of all groups of animals, plants, and microorganisms, their structures follow a limited number of general themes; spherical or cylindrical shells built of hundreds of repeated protein subunits enclosing a nucleic acid - DNA or RNA - genome. Since the 1960s it has been known that the protein shells of spherical viruses in fact conform to icosahedral symmetry or to subtle deviations from icosahedral symmetry. The construction of the shell lattices and the transformations they go through in the different stages of the viral life cycle are not fully understood. The shells contain the nucleicmore » in a highly condensed state, of unknown coiling/organization. Features of the well studied bacterial viruses will be reviewed, with examples from adenoviruses, herpesviruses, poliovirus, and HIV. The emergence of new viral disease has led to increased interest in the development of agents which interfere with virus reproduction at the level of the assembly or function of the organized particle. Recently computational approaches to the problem of virus assembly have made important contributions to clarifying shell assembly processes. 1 ref.« less

Air-stable nZVI formation mediated by glutamic acid: solid-state storable material exhibiting 2D chain morphology and high reactivity in aqueous environment

NASA Astrophysics Data System (ADS)

Siskova, Karolina; Tucek, Jiri; Machala, Libor; Otyepkova, Eva; Filip, Jan; Safarova, Klara; Pechousek, Jiri; Zboril, Radek

2012-03-01

We report a new chemical approach toward air-stable nanoscale zero-valent iron (nZVI). The uniformly sized (approx. 80 nm) particles, formed by the reduction of Fe(II) salt by borohydride in the presence of glutamic acid, are coated by a thin inner shell of amorphous ferric oxide/hydroxide and a secondary shell consisting of glutamic acid. The as-prepared nanoparticles stabilized by the inorganic-organic double shell create 2D chain morphologies. They are storable for several months under ambient atmosphere without the loss of Fe(0) relative content. They show one order of magnitude higher rate constant for trichlorethene decomposition compared with the pristine particles possessing only the inorganic shell as a protective layer. This is the first example of the inorganic-organic (consisting of low-molecular weight species) double-shell stabilized nanoscale zero-valent iron material being safely transportable in solid-state, storable on long-term basis under ambient conditions, environmentally acceptable for in situ applications, and extraordinarily reactive if contacted with reducible pollutants, all in one.

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.

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.

Sea Hare Aplysia punctata (Mollusca: Gastropoda) Can Maintain Shell Calcification under Extreme Ocean Acidification.

PubMed

Carey, Nicholas; Dupont, Sam; Sigwart, Julia D

2016-10-01

Ocean acidification is expected to cause energetic constraints upon marine calcifying organisms such as molluscs and echinoderms, because of the increased costs of building or maintaining shell material in lower pH. We examined metabolic rate, shell morphometry, and calcification in the sea hare Aplysia punctata under short-term exposure (19 days) to an extreme ocean acidification scenario (pH 7.3, ∼2800 μatm pCO 2 ), along with a group held in control conditions (pH 8.1, ∼344 μatm pCO 2 ). This gastropod and its congeners are broadly distributed and locally abundant grazers, and have an internal shell that protects the internal organs. Specimens were examined for metabolic rate via closed-chamber respirometry, followed by removal and examination of the shell under confocal microscopy. Staining using calcein determined the amount of new calcification that occurred over 6 days at the end of the acclimation period. The width of new, pre-calcified shell on the distal shell margin was also quantified as a proxy for overall shell growth. Aplysia punctata showed a 30% reduction in metabolic rate under low pH, but calcification was not affected. This species is apparently able to maintain calcification rate even under extreme low pH, and even when under the energetic constraints of lower metabolism. This finding adds to the evidence that calcification is a largely autonomous process of crystallization that occurs as long as suitable haeomocoel conditions are preserved. There was, however, evidence that the accretion of new, noncalcified shell material may have been reduced, which would lead to overall reduced shell growth under longer-term exposures to low pH independent of calcification. Our findings highlight that the chief impact of ocean acidification upon the ability of marine invertebrates to maintain their shell under low pH may be energetic constraints that hinder growth of supporting structure, rather than maintenance of calcification.

Testing the best method to prepare recent and fossil brachiopod shells for SEM analysis

NASA Astrophysics Data System (ADS)

Crippa, Gaia; Ye, Facheng

2017-04-01

The analysis of shell microstructures by Scanning Electron Microscope (SEM) is a method easily available to most palaeontologists and geochemists. This kind of analysis is a fundamental step in the study of the mineralised parts of marine and terrestrial organisms, and it provides invaluable information in different fields of palaeontology, from the comprehension of evolutionary taxonomy and biomineralisation processes to the screening of shell diagenetic alteration. In precipitating their low-magnesium calcite shells in isotopic equilibrium with ambient seawater, brachiopods are excellent archives of past seawater temperature and ocean chemistry. However, diagenetic processes may alter the original fabric and the original geochemical composition of the shells; the SEM analysis of the microstructure represents one of the most common method used to test fossil shell preservation and eventually exclude diagenetic alteration. Notwithstanding the importance of this analysis, only few and scattered data have been published about the preparation and cleaning of brachiopod shells for SEM analyses Here, we describe several tests performed on recent and fossil brachiopod shells, experimenting new and old methodologies in order to identify a general protocol to better highlight and analyze the shell fabric. Recent taxa include Liothyrella uva and Liothyrella neozelanica, respectively collected from Antarctica and New Zealand; fossil shells are those of Terebratula scillae collected from the lower Pleistocene Stirone River sedimentary succession in Northern Italy. We carried out several tests to check the response of the shell fabric to the resin used to embed the valves before cutting and to different times of exposure to hydrochloric acid; furthermore, as the presence of the organic matrix in recent shells represents the main obstacle to obtaining high quality SEM images, we used bleach and hydrogen peroxide with different concentrations and times of exposure to remove it. We conclude that bleach and hydrogen peroxide at the highest time of exposure followed by hydrochloric acid for 3 seconds is the best method to use when preparing recent brachiopods, whereas fossil shells should undergo higher exposure time to hydrochloric acid (15 seconds).

An Eocene orthocone from Antarctica shows convergent evolution of internally shelled cephalopods

PubMed Central

Bengtson, Stefan; Reguero, Marcelo A.; Mörs, Thomas

2017-01-01

Background The Subclass Coleoidea (Class Cephalopoda) accommodates the diverse present-day internally shelled cephalopod mollusks (Spirula, Sepia and octopuses, squids, Vampyroteuthis) and also extinct internally shelled cephalopods. Recent Spirula represents a unique coleoid retaining shell structures, a narrow marginal siphuncle and globular protoconch that signify the ancestry of the subclass Coleoidea from the Paleozoic subclass Bactritoidea. This hypothesis has been recently supported by newly recorded diverse bactritoid-like coleoids from the Carboniferous of the USA, but prior to this study no fossil cephalopod indicative of an endochochleate branch with an origin independent from subclass Bactritoidea has been reported. Methodology/Principal findings Two orthoconic conchs were recovered from the Early Eocene of Seymour Island at the tip of the Antarctic Peninsula, Antarctica. They have loosely mineralized organic-rich chitin-compatible microlaminated shell walls and broadly expanded central siphuncles. The morphological, ultrustructural and chemical data were determined and characterized through comparisons with extant and extinct taxa using Scanning Electron Microscopy/Energy Dispersive Spectrometry (SEM/EDS). Conclusions/Significance Our study presents the first evidence for an evolutionary lineage of internally shelled cephalopods with independent origin from Bactritoidea/Coleoidea, indicating convergent evolution with the subclass Coleoidea. A new subclass Paracoleoidea Doguzhaeva n. subcl. is established for accommodation of orthoconic cephalopods with the internal shell associated with a broadly expanded central siphuncle. Antarcticerida Doguzhaeva n. ord., Antarcticeratidae Doguzhaeva n. fam., Antarcticeras nordenskjoeldi Doguzhaeva n. gen., n. sp. are described within the subclass Paracoleoidea. The analysis of organic-rich shell preservation of A. nordenskjoeldi by use of SEM/EDS techniques revealed fossilization of hyposeptal cameral soft tissues. This suggests that a depositional environment favoring soft-tissue preservation was the factor enabling conservation of the weakly mineralized shell of A. nordenskjoeldi. PMID:28248970

Stereo and scanning electron microscopy of in-shell Brazil nut (Bertholletia excelsa H.B.K.): part two-surface sound nut fungi spoilage susceptibility.

PubMed

Scussel, Vildes M; Manfio, Daniel; Savi, Geovana D; Moecke, Elisa H S

2014-11-01

This work reports the in-shell Brazil nut spoilage susceptible morpho-histological characteristics and fungi infection (shell, edible part, and brown skin) through stereo and scanning electron microscopies (SEM). The following characteristics related to shell (a) morphology-that allow fungi and insects' entrance to inner nut, and (b) histology-that allow humidity absorption, improving environment conditions for living organisms development, were identified. (a.1) locule in testae-the nut navel, which is a cavity formed during nut detaching from pods (located at 1.0 to 2.0/4th of the shell B&C nut faces linkage). It allows the nut brown skin (between shell and edible part) first contact to the external environment, through the (a.2) nut channel-the locule prolongation path, which has the water/nutrients cambium function for their transport and distribution to the inner seed (while still on the tree/pod). Both, locule followed by the channel, are the main natural entrance of living organisms (fungi and insects), including moisture to the inner seed structures. In addition, the (a.3) nut shell surface-which has a crinkled and uneven surface morphology-allows water absorption, thus adding to the deterioration processes too. The main shell histological characteristic, which also allows water absorption (thus improving environment conditions for fungi proliferation), is the (b.1) cell wall porosity-the multilayered wall and porous rich cells that compose the shell faces double tissue layers and the (b.2) soft tissue-the mix of tissues 2 faces corner/linkage. This work also shows in details the SEM nut spoilage susceptible features highly fungi infected with hyphae and reproductive structures distribution. © 2014 Institute of Food Technologists®

Metal-Organic Frameworks Derived Porous Core/Shell Structured ZnO/ZnCo2O4/C Hybrids as Anodes for High-Performance Lithium-Ion Battery.

PubMed

Ge, Xiaoli; Li, Zhaoqiang; Wang, Chengxiang; Yin, Longwei

2015-12-09

Metal-organic frameworks (MOFs) derived porous core/shell ZnO/ZnCo2O4/C hybrids with ZnO as a core and ZnCo2O4 as a shell are for the first time fabricated by using core/shell ZnCo-MOF precursors as reactant templates. The unique MOFs-derived core/shell structured ZnO/ZnCo2O4/C hybrids are assembled from nanoparticles of ZnO and ZnCo2O4, with homogeneous carbon layers coated on the surface of the ZnCo2O4 shell. When acting as anode materials for lithium-ion batteries (LIBs), the MOFs-derived porous ZnO/ZnCo2O4/C anodes exhibit outstanding cycling stability, high Coulombic efficiency, and remarkable rate capability. The excellent electrochemical performance of the ZnO/ZnCo2O4/C LIB anodes can be attributed to the synergistic effect of the porous structure of the MOFs-derived core/shell ZnO/ZnCo2O4/C and homogeneous carbon layer coating on the surface of the ZnCo2O4 shells. The hierarchically porous core/shell structure offers abundant active sites, enhances the electrode/electrolyte contact area, provides abundant channels for electrolyte penetration, and also alleviates the structure decomposition induced by Li(+) insertion/extraction. The carbon layers effectively improve the conductivity of the hybrids and thus enhance the electron transfer rate, efficiently prevent ZnCo2O4 from aggregation and disintegration, and partially buffer the stress induced by the volume change during cycles. This strategy may shed light on designing new MOF-based hybrid electrodes for energy storage and conversion devices.

Room-temperature synthesis of core-shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins.

PubMed

Lin, Guo; Gao, Chaohong; Zheng, Qiong; Lei, Zhixian; Geng, Huijuan; Lin, Zian; Yang, Huanghao; Cai, Zongwei

2017-03-28

Core-shell structured magnetic covalent organic frameworks (Fe 3 O 4 @COFs) were synthesized via a facile approach at room temperature. Combining the advantages of high porosity, magnetic responsiveness, chemical stability and selectivity, Fe 3 O 4 @COFs can serve as an ideal absorbent for the highly efficient enrichment of peptides and the simultaneous exclusion of proteins from complex biological samples.

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.

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)

Understanding to Hierarchical Microstructures of Crab (Chinese hairy) Shell as a Natural Architecture

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

Chuanqiang, Zhou; Xiangxiang, Gong; School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou

This work was done to better understand the microstructures, composition and mechanical properties of Chinese hairy crab shell. For fully revealing its hierarchical microstructure, the crab shell was observed with electron microscope under different magnifications from different facets. XRD, EDS, FTIR and TGA techniques have been used to characterize the untreated and chemically-treated crab shells, which provided enough information to determine the species and relative content of components in this biomaterial. Combined the microstructures with constituents analysis, the structural principles of crab shell was detailedly realized from different structural levels beyond former reports. To explore the relationship between structure andmore » function, the mechanical properties of shell have been measured through performing tensile tests. The contributions of organics and minerals in shell to the mechanical properties were also discussed by measuring the tensile strength of de-calcification samples treated with HCl solution.« less

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

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.

Glass shell manufacturing in space

NASA Technical Reports Server (NTRS)

Downs, R. L.; Ebner, M. A.; Nolen, R. L., Jr.

1981-01-01

Highly-uniform, hollow glass spheres (shells), which are used for inertial confinement fusion targets, were formed from metal-organic gel powder feedstock in a vertical furnace. As a result of the rapid pyrolysis caused by the furnace, the gel is transformed to a shell in five distinct stages: (a) surface closure of the porous gel; (b) generation of a closed-cell foam structure in the gel; (c) spheridization of the gel and further expansion of the foam; (d) coalescence of the closed-cell foam to a single-void shell; and (e) fining of the glass shell. The heat transfer from the furnace to the falling gel particle was modeled to determine the effective heating rate of the gel. The model predicts the temperature history for a particle as a function of mass, dimensions, specific heat, and absorptance as well as furnace temperature profile and thermal conductivity of the furnace gas. A model was developed that predicts the gravity-induced degradation of shell concentricity in falling molten shells as a function of shell characteristics and time.

PMMA/PS coaxial electrospinning: core-shell fiber morphology as a function of material parameters

NASA Astrophysics Data System (ADS)

Rahmani, Shahrzad; Arefazar, Ahmad; Latifi, Masoud

2017-03-01

Core-shell fibers of polymethyl methacrylate (PMMA) and polystyrene (PS) have been successfully electrospun by coaxial electrospinning. To evaluate the influence of the solvent on the final fiber morphology, four types of organic solvents were used in the shell solution while the core solvent was preserved. Morphological observations with scanning electron microscopy, transmission electron microscopy and optical microscopy revealed that both core and shell solvent properties were involved in the final fiber morphology. To explain this involvement, alongside a discussion of the Bagley solubility graph of PS and PMMA, a novel criterion based on solvent physical properties was introduced. A theoretical model based on the momentum conservation principle was developed and applied for describing the dependence of the core and shell diameters to their solvent combinations. Different concentrations of core and shell were also investigated in the coaxial electrospinning of PMMA/PS. The core-shell fiber morphologies with different core and shell concentrations were compared with their single electrospun fibers.

Microcapsule and methods of making and using microcapsules

DOEpatents

Okawa, David C.; Pastine, Stefan J.; Zettl, Alexander K.; Frechet, Jean M.J.

2014-09-02

An embodiment of a microcapsule includes a shell surrounding a space, a liquid within the shell, and a light absorbing material within the liquid. An embodiment of a method of making microcapsules includes forming a mixture of a light absorbing material and an organic solution. An emulsion of the mixture and an aqueous solution is then formed. A polymerization agent is added to the emulsion, which causes microcapsules to be formed. Each microcapsule includes a shell surrounding a space, a liquid within the shell, and light absorbing material within the liquid. An embodiment of a method of using microcapsules includes providing phototriggerable microcapsules within a bulk material. Each of the phototriggerable microcapsules includes a shell surrounding a space, a chemically reactive material within the shell, and a light absorbing material within the shell. At least some of the phototriggerable microcapsules are exposed to light, which causes the chemically reactive material to release from the shell and to come into contact with bulk material.

Intermediate-band photosensitive device with quantum dots having tunneling barrier embedded in organic matrix

DOEpatents

Forrest, Stephen R.

2008-08-19

A plurality of quantum dots each have a shell. The quantum dots are embedded in an organic matrix. At least the quantum dots and the organic matrix are photoconductive semiconductors. The shell of each quantum dot is arranged as a tunneling barrier to require a charge carrier (an electron or a hole) at a base of the tunneling barrier in the organic matrix to perform quantum mechanical tunneling to reach the respective quantum dot. A first quantum state in each quantum dot is between a lowest unoccupied molecular orbital (LUMO) and a highest occupied molecular orbital (HOMO) of the organic matrix. Wave functions of the first quantum state of the plurality of quantum dots may overlap to form an intermediate band.

An EAV-HP Insertion in 5′ Flanking Region of SLCO1B3 Causes Blue Eggshell in the Chicken

PubMed Central

Yang, Xiaolin; Li, Guangqi; Zhang, Yuanyuan; Li, Junying; Wang, Xiaotong; Bai, Jirong; Xu, Guiyun; Deng, Xuemei; Yang, Ning; Wu, Changxin

2013-01-01

The genetic determination of eggshell coloration has not been determined in birds. Here we report that the blue eggshell is caused by an EAV-HP insertion that promotes the expression of SLCO1B3 gene in the uterus (shell gland) of the oviduct in chicken. In this study, the genetic map location of the blue eggshell gene was refined by linkage analysis in an F2 chicken population, and four candidate genes within the refined interval were subsequently tested for their expression levels in the shell gland of the uterus from blue-shelled and non-blue-shelled hens. SLCO1B3 gene was found to be the only one expressed in the uterus of blue-shelled hens but not in that of non-blue-shelled hens. Results from a pyrosequencing analysis showed that only the allele of SLCO1B3 from blue-shelled chickens was expressed in the uterus of heterozygous hens (O*LC/O*N). SLCO1B3 gene belongs to the organic anion transporting polypeptide (OATP) family; and the OATPs, functioning as membrane transporters, have been reported for the transportation of amphipathic organic compounds, including bile salt in mammals. We subsequently resequenced the whole genomic region of SLCO1B3 and discovered an EAV-HP insertion in the 5′ flanking region of SLCO1B3. The EAV-HP insertion was found closely associated with blue eggshell phenotype following complete Mendelian segregation. In situ hybridization also demonstrated that the blue eggshell is associated with ectopic expression of SLCO1B3 in shell glands of uterus. Our finding strongly suggests that the EAV-HP insertion is the causative mutation for the blue eggshell phenotype. The insertion was also found in another Chinese blue-shelled breed and an American blue-shelled breed. In addition, we found that the insertion site in the blue-shelled chickens from Araucana is different from that in Chinese breeds, which implied independent integration events in the blue-shelled chickens from the two continents, providing a parallel evolutionary example at the molecular level. PMID:23359636

Outer organic layer and internal repair mechanism protects pteropod Limacina helicina from ocean acidification

NASA Astrophysics Data System (ADS)

Peck, Victoria L.; Tarling, Geraint A.; Manno, Clara; Harper, Elizabeth M.; Tynan, Eithne

2016-05-01

Scarred shells of polar pteropod Limacina helicina collected from the Greenland Sea in June 2012 reveal a history of damage, most likely failed predation, in earlier life stages. Evidence of shell fracture and subsequent re-growth is commonly observed in specimens recovered from the sub-Arctic and further afield. However, at one site within sea-ice on the Greenland shelf, shells that had been subject to mechanical damage were also found to exhibit considerable dissolution. It was evident that shell dissolution was localised to areas where the organic, periostracal sheet that covers the outer shell had been damaged at some earlier stage during the animal's life. Where the periostracum remained intact, the shell appeared pristine with no sign of dissolution. Specimens which appeared to be pristine following collection were incubated for four days. Scarring of shells that received periostracal damage during collection only became evident in specimens that were incubated in waters undersaturated with respect to aragonite, ΩAr≤1. While the waters from which the damaged specimens were collected at the Greenland Sea sea-ice margin were not ΩAr≤1, the water column did exhibit the lowest ΩAr values observed in the Greenland and Barents Seas, and was likely to have approached ΩAr≤1 during the winter months. We demonstrate that L. helicina shells are only susceptible to dissolution where both the periostracum has been breached and the aragonite beneath the breach is exposed to waters of ΩAr≤1. Exposure of multiple layers of aragonite in areas of deep dissolution indicate that, as with many molluscs, L. helicina is able to patch up dissolution damage to the shell by secreting additional aragonite internally and maintain their shell. We conclude that, unless breached, the periostracum provides an effective shield for pteropod shells against dissolution in waters ΩAr≤1, and when dissolution does occur the animal has an effective means of self-repair. We suggest that future studies of pteropod shell condition are undertaken on specimens from which the periostracum has not been removed in preparation.

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.

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

NASA Astrophysics Data System (ADS)

Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

2017-03-01

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days. Newly formed calcite nucleated at locations which were in contact with the fluid, at the shell surface, in the open pore system, and along growth lines. In the experiments with fluids simulating meteoric water, calcite crystals reached sizes up to 200 µm, while in the experiments with Mg-containing fluids the calcite crystals reached sizes up to 1 mm after 7 days of alteration. Aragonite is metastable at all applied conditions. Only a small bulk thermodynamic driving force exists for the transition to calcite. We attribute the sluggish replacement reaction to the inhibition of calcite nucleation in the temperature window from ca. 50 to ca. 170 °C or, additionally, to the presence of magnesium. Correspondingly, in Mg2+-bearing solutions the newly formed calcite crystals are larger than in Mg2+-free solutions. Overall, the aragonite-calcite transition occurs via an interface-coupled dissolution-reprecipitation mechanism, which preserves morphologies down to the sub-micrometre scale and induces porosity in the newly formed phase. The absence of aragonite replacement by calcite at temperatures lower than 175 °C contributes to explaining why aragonitic or bimineralic shells and skeletons have a good potential of preservation and a complete fossil record.

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

PubMed

Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

2017-08-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A mineralogical record of ocean change: Decadal and centennial patterns in the California mussel.

PubMed

McCoy, Sophie J; Kamenos, Nicholas A; Chung, Peter; Wootton, Timothy J; Pfister, Catherine A

2018-06-01

Ocean acidification, a product of increasing atmospheric carbon dioxide, may already have affected calcified organisms in the coastal zone, such as bivalves and other shellfish. Understanding species' responses to climate change requires the context of long-term dynamics. This can be particularly difficult given the longevity of many important species in contrast with the relatively rapid onset of environmental changes. Here, we present a unique archival dataset of mussel shells from a locale with recent environmental monitoring and historical climate reconstructions. We compare shell structure and composition in modern mussels, mussels from the 1970s, and mussel shells dating back to 1000-2420 years BP. Shell mineralogy has changed dramatically over the past 15 years, despite evidence for consistent mineral structure in the California mussel, Mytilus californianus, over the prior 2500 years. We present evidence for increased disorder in the calcium carbonate shells of mussels and greater variability between individuals. These changes in the last decade contrast markedly from a background of consistent shell mineralogy for centuries. Our results use an archival record of natural specimens to provide centennial-scale context for altered minerology and variability in shell features as a response to acidification stress and illustrate the utility of long-term studies and archival records in global change ecology. Increased variability between individuals is an emerging pattern in climate change responses, which may equally expose the vulnerability of organisms and the potential of populations for resilience. © 2017 John Wiley & Sons Ltd.

The Shell of the Invasive Bivalve Species Dreissena polymorpha: Biochemical, Elemental and Textural Investigations

PubMed Central

Broussard, Cédric; Catherinet, Bastien; Plasseraud, Laurent; Alcaraz, Gérard; Bundeleva, Irina; Marin, Frédéric

2016-01-01

The zebra mussel Dreissena polymorpha is a well-established invasive model organism. Although extensively used in environmental sciences, virtually nothing is known of the molecular process of its shell calcification. By describing the microstructure, geochemistry and biochemistry/proteomics of the shell, the present study aims at promoting this species as a model organism in biomineralization studies, in order to establish a bridge with ecotoxicology, while sketching evolutionary conclusions. The shell of D. polymorpha exhibits the classical crossed-lamellar/complex crossed lamellar combination found in several heterodont bivalves, in addition to an external thin layer, the characteristics of which differ from what was described in earlier publication. We show that the shell selectively concentrates some heavy metals, in particular uranium, which predisposes D. polymorpha to local bioremediation of this pollutant. We establish the biochemical signature of the shell matrix, demonstrating that it interacts with the in vitro precipitation of calcium carbonate and inhibits calcium carbonate crystal formation, but these two properties are not strongly expressed. This matrix, although overall weakly glycosylated, contains a set of putatively calcium-binding proteins and a set of acidic sulphated proteins. 2D-gels reveal more than fifty proteins, twenty of which we identify by MS-MS analysis. We tentatively link the shell protein profile of D. polymorpha and the peculiar recent evolution of this invasive species of Ponto-Caspian origin, which has spread all across Europe in the last three centuries. PMID:27213644

Adding teeth to wave action: the destructive effects of wave-borne rocks on intertidal organisms.

PubMed

Shanks, Alan L; Wright, William G

1986-06-01

Observations in rocky intertidal areas demonstrate that breaking waves 'throw' rocks and cobbles and that these missiles can damage and kill organisms. Targets in the intertidal were dented by impacts from wave-borne rocks. New dents/day in these targets was positively correlated with the daily maximum significant wave height and with new patches/day in aggregations of the barnacle Chthamalus fissus. Impact frequency was highest in the upper intertidal and varied dramatically between microhabitats on individual boulders (edges, tops and faces). These patterns were reflected in the microhabitat abundances of 'old' and 'young' barnacles. Comparisons were made of the survivorship and the frequency of shell damage in two populations of the limpet Lottia gigantea living in habitats which differed primarily in the number of moveable rocks (i.e. potential projectiles). The mortality rate and frequency of shell damage were significantly higher in the projectilerich habitat. In addition only in this habitat did the frequency of shell damage covary significantly with seasonal periods of high surf. Investigation of the response of limpet shells to impacts suggests that shell strength varies between species and increases with shell size. Species-specific patterns of non-fatal shell breakage may have evolved to absorb the energy of impacts. In two of the intertidal habitats studied, wave-borne rock damage was chronic and, at least in part, may have governed the faunal makeup of the community by contributing to the physical 'boundaries" of the environment within which the inhabitants must survive.

Core-shell nanophosphor architecture: toward efficient energy transport in inorganic/organic hybrid solar cells.

PubMed

Li, Qinghua; Yuan, Yongbiao; Chen, Zihan; Jin, Xiao; Wei, Tai-huei; Li, Yue; Qin, Yuancheng; Sun, Weifu

2014-08-13

In this work, a core-shell nanostructure of samarium phosphates encapsulated into a Eu(3+)-doped silica shell has been successfully fabricated, which has been confirmed by X-ray diffraction, transmission electron microscopy (TEM), and high-resolution TEM. Moreover, we report the energy transfer process from the Sm(3+) to emitters Eu(3+) that widens the light absorption range of the hybrid solar cells (HSCs) and the strong enhancement of the electron-transport of TiO2/poly(3-hexylthiophene) (P3HT) bulk heterojunction (BHJ) HSCs by introducing the unique core-shell nanoarchitecture. Furthermore, by applying femtosecond transient absorption spectroscopy, we successfully obtain the electron transport lifetimes of BHJ systems with or without incorporating the core-shell nanophosphors (NPs). Concrete evidence has been provided that the doping of core-shell NPs improves the efficiency of electron transfers from donor to acceptor, but the hole transport almost remains unchanged. In particular, the hot electron transfer lifetime was shortened from 30.2 to 16.7 ps, i.e., more than 44% faster than pure TiO2 acceptor. Consequently, a notable power conversion efficiency of 3.30% for SmPO4@Eu(3+):SiO2 blended TiO2/P3HT HSCs is achieved at 5 wt % as compared to 1.98% of pure TiO2/P3HT HSCs. This work indicates that the core-shell NPs can efficiently broaden the absorption region, facilitate electron-transport of BHJ, and enhance photovoltaic performance of inorganic/organic HSCs.

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.

How to best smash a snail: the effect of tooth shape on crushing load

PubMed Central

Crofts, S. B.; Summers, A. P.

2014-01-01

Organisms that are durophagous, hard prey consumers, have a diversity of tooth forms. To determine why we see this variation, we tested whether some tooth forms break shells better than others. We measured the force needed with three series of aluminium tooth models, which varied in concavity and the morphology of a stress concentrating cusp, to break a shell. We created functionally identical copies of two intertidal snail shells: the thicker shelled Nucella ostrina and the more ornamented Nucella lamellosa using a three-dimensional printer. In this way, we reduced variation in material properties between test shells, allowing us to test only the interaction of the experimental teeth with the two shell morphologies. We found that for all tooth shapes, thicker shells are harder to break than the thinner shells and that increased ornamentation has no discernible effect. Our results show that for both shell morphologies, domed and flat teeth break shells better than cupped teeth, and teeth with tall or skinny cusps break shells best. While our results indicate that there is an ideal tooth form for shell breaking, we do not see this shape in nature. This suggests a probable trade-off between tooth function and the structural integrity of the tooth. PMID:24430124

Biomineral repair of abalone shell apertures.

PubMed

Cusack, Maggie; Guo, Dujiao; Chung, Peter; Kamenos, Nicholas A

2013-08-01

The shell of the gastropod mollusc, abalone, is comprised of nacre with an outer prismatic layer that is composed of either calcite or aragonite or both, depending on the species. A striking characteristic of the abalone shell is the row of apertures along the dorsal margin. As the organism and shell grow, new apertures are formed and the preceding ones are filled in. Detailed investigations, using electron backscatter diffraction, of the infill in three species of abalone: Haliotis asinina, Haliotis gigantea and Haliotis rufescens reveals that, like the shell, the infill is composed mainly of nacre with an outer prismatic layer. The infill prismatic layer has identical mineralogy as the original shell prismatic layer. In H. asinina and H. gigantea, the prismatic layer of the shell and infill are made of aragonite while in H. rufescens both are composed of calcite. Abalone builds the infill material with the same high level of biological control, replicating the structure, mineralogy and crystallographic orientation as for the shell. The infill of abalone apertures presents us with insight into what is, effectively, shell repair. Copyright © 2013 Elsevier Inc. All rights reserved.

[Effects of stabilization treatment on migration and transformation of heavy metals in mineral waste residues].

PubMed

Zhao, Shu-Hua; Chen, Zhi-Liang; Zhang, Tai-Ping; Pan, Wei-Bin; Peng, Xiao-Chun; Che, Rong; Ou, Ying-Juan; Lei, Guo-Jian; Zhou, Ding

2014-04-01

Different forms of heavy metals in soil will produce different environmental effects, and will directly influence the toxicity, migration and bioavailability of heavy metals. This study used lime, fly ash, dried sludge, peanut shells as stabilizers in the treatment of heavy metals in mineral waste residues. Morphological analyses of heavy metal, leaching experiments, potted plant experiments were carried out to analyze the migration and transformation of heavy metals. The results showed that after adding stabilizers, the pH of the acidic mineral waste residues increased to more than neutral, and the organic matter content increased significantly. The main existing forms of As, Pb, and Zn in the mineral waste residues were the residual. The contents of exchangeable and organic matter-bound As decreased by 65.6% and 87.7% respectively after adding fly ash, dried sludge and peanut shells. Adding lime, fly ash and peanut shells promoted the transformation of As from the Fe-Mn oxide-bound to the carbonate-bound, and adding lime and fly ash promoted the transformation of Pb and Zn from the exchangeable, Fe-Mn oxide-bound, organic matter-bound to the residual. After the early stage of the stabilization treatment, the contents of As, Pb and Zn in the leachate had varying degrees of decline, and adding peanut shells could reduce the contents of As, Pb and Zn in the leachate further. Among them, the content of As decreased most significantly after treatment with fly ash, dried sludge and peanut shells, with a decline of 57.4%. After treatment with lime, fly ash and peanut shells, the content of Zn decreased most significantly, by 24.9%. The addition of stabilizers was advantageous to the germination and growth of plants. The combination of fly ash, dried sludge and peanut shell produced the best effect, and the Vetiveria zizanioides germination rate reached 76% in the treated wasted mineral residues.

Engineering and sustainability aspect of palm oil shell powder in cement

NASA Astrophysics Data System (ADS)

Karim, Mohammad Razaul; Hossain, Md. Moktar; Yusoff, Sumiani Binti

2017-06-01

Palm oil shell (POS) is a waste material which significantly produced in palm oil mills. In current practice, this waste is dumped in open land or landfill sites or is used as fuel to run a steam turbine of a boiler, which leads to environmental pollutions. The characterization, engineering and sustainability aspect of this waste for using in cement-based applications lead to reduce the emission of carbon dioxide and cost, save natural resources for cement production and also sustainable usage of waste material. The characterization was carried out using particle size analyzer, XRF, SEM and total organic carbon analyzer. ASTM standard methods were used to observe the setting time and water for normal consistency. The compressive strength of palm oil shell powder (POSP) blended cement was explored with the water to cement and cement to sand ratio of 0.40 and 0.50, respectively up to 40% replacement levels of OPC. Result found that the setting time and water demand were increased, but compressive strength was decreased to replacement levels. However, the incorporation of POSP in cement was reduced 9.6% of CO2 emission, 25 % of the cost and save natural resource, i.e. limestone, clay, iron ore, silica shale and gypsum of 35.1%, 4.95%, 0.9%, 4.05 % and 1.2 %, respectively at 30% replacement level of OPC. The results of this extensive study on POSP characterization, effect on basic cement properties and sustainability aspect provide the guidance for using the POSP at industrial scale for cement production.

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

Revealing weak spin-orbit coupling effects on charge carriers in a π -conjugated polymer

NASA Astrophysics Data System (ADS)

Malissa, H.; Miller, R.; Baird, D. L.; Jamali, S.; Joshi, G.; Bursch, M.; Grimme, S.; van Tol, J.; Lupton, J. M.; Boehme, C.

2018-04-01

We measure electrically detected magnetic resonance on organic light-emitting diodes made of the polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] at room temperature and high magnetic fields where spectral broadening of the resonance due to spin-orbit coupling (SOC) exceeds that due to the local hyperfine fields. Density-functional-theory calculations on an open-shell model of the material reveal g -tensors of charge-carrier spins in the lowest unoccupied (electron) and highest occupied (hole) molecular orbitals. These tensors are used for simulations of magnetic resonance line shapes. Besides providing the first quantification and direct observation of SOC effects on charge-carrier states in these weakly SO-coupled hydrocarbons, this procedure demonstrates that spin-related phenomena in these materials are fundamentally monomolecular in nature.

In vitro growth of flat aragonite crystals between the layers of the insoluble organic matrix of the abalone Haliotis laevigata

NASA Astrophysics Data System (ADS)

Gries, Katharina I.; Heinemann, Fabian; Rosenauer, Andreas; Fritz, Monika

2012-11-01

Nacre of abalone shells consists of aragonite platelets and organic material, the so-called organic matrix. During the growth process of the shell the aragonite platelets grow into a scaffold formed by the organic matrix. In this work we tried to mimic this growth process by placing a piece of the insoluble organic matrix (which is a part of the organic matrix) of the abalone Haliotis laevigata in a crystallization device which was flowed through by CaCl2 and NaHCO3 solutions. Using this setup amongst others flat aragonite crystals grow on the insoluble organic matrix. When investigating these crystals in a transmission electron microscope it is possible to recognize similarities to the structure of nacre, like the formation of mineral bridges and growth between layers of the insoluble organic matrix. These similarities are presented in this paper.

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.

Non-empirical Prediction of the Photophysical and Magnetic Properties of Systems with Open d- and f-Shells Based on Combined Ligand Field and Density Functional Theory (LFDFT).

PubMed

Daul, Claude

2014-09-01

Despite the important growth of ab initio and computational techniques, ligand field theory in molecular science or crystal field theory in condensed matter offers the most intuitive way to calculate multiplet energy levels arising from systems with open shells d and/or f electrons. Over the past decade we have developed a ligand field treatment of inorganic molecular modelling taking advantage of the dominant localization of the frontier orbitals within the metal-sphere. This feature, which is observed in any inorganic coordination compound, especially if treated by Density Functional Theory calculation, allows the determination of the electronic structure and properties with a surprising good accuracy. In ligand field theory, the theoretical concepts consider only a single atom center; and treat its interaction with the chemical environment essentially as a perturbation. Therefore success in the simple ligand field theory is no longer questionable, while the more accurate molecular orbital theory does in general over-estimate the metal-ligand covalence, thus yields wave functions that are too delocalized. Although LF theory has always been popular as a semi-empirical method when dealing with molecules of high symmetry e.g. cubic symmetry where the number of parameters needed is reasonably small (3 or 5), this is no more the case for molecules without symmetry and involving both an open d- and f-shell (# parameters ∼90). However, the combination of LF theory and Density Functional (DF) theory that we introduced twenty years ago can easily deal with complex molecules of any symmetry with two and more open shells. The accuracy of these predictions from 1(st) principles achieves quite a high accuracy (<5%) in terms of states energies. Hence, this approach is well suited to predict the magnetic and photo-physical properties arbitrary molecules and materials prior to their synthesis, which is the ultimate goal of each computational chemist. We will illustrate the performance of LFDFT for the design of phosphors that produces light similar to our sun and predict the magnetic anisotropy energy of single ion magnets.

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

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.

76 FR 59756 - Self-Regulatory Organizations; New York Stock Exchange LLC; Notice of Designation of a Longer...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-27

... of a ``Reverse Merger'' With a Shell Company September 21, 2011. On July 22, 2011, New York Stock... after consummation of a ``reverse merger'' with a shell company. The proposed rule change was published...'' [[Page 59757

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).

Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): structure and electron irradiation effects.

PubMed

Gontard, Lionel C; Fernández, Asunción; Dunin-Borkowski, Rafal E; Kasama, Takeshi; Lozano-Pérez, Sergio; Lucas, Stéphane

2014-12-01

Hybrid (organic shell-inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C3H5NH2. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

A rule-based shell to hierarchically organize HST observations

NASA Technical Reports Server (NTRS)

Bose, Ashim; Gerb, Andrew

1995-01-01

An observing program on the Hubble Space Telescope (HST) is described in terms of exposures that are obtained by one or more of the instruments onboard the HST. These exposures are organized into a hierarchy of structures for purposes of efficient scheduling of observations. The process by which exposures get organized into the higher-level structures is called merging. This process relies on rules to determine which observations can be 'merged' into the same higher level structure, and which cannot. The TRANSformation expert system converts proposals for astronomical observations with HST into detailed observing plans. The conversion process includes the task of merging. Within TRANS, we have implemented a declarative shell to facilitate merging. This shell offers the following features: (1) an easy way of specifying rules on when to merge and when not to merge, (2) a straightforward priority mechanism for resolving conflicts among rules, (3) an explanation facility for recording the merging history, (4) a report generating mechanism to help users understand the reasons for merging, and (5) a self-documenting mechanism that documents all the merging rules that have been defined in the shell, ordered by priority. The merging shell is implemented using an object-oriented paradigm in CLOS. It has been a part of operational TRANS (after extensive testing) since July 1993. It has fulfilled all performance expectations, and has considerably simplified the process of implementing new or changed requirements for merging. The users are pleased with its report-generating and self-documenting features.

Characterization of core–shell MOF particles by depth profiling experiments using on-line single particle mass spectrometry

DOE PAGES

Cahill, J. F.; Fei, H.; Cohen, S. M.; ...

2015-01-05

Materials with core-shell structures have distinct properties that lend themselves to a variety of potential applications. Characterization of small particle core-shell materials presents a unique analytical challenge. Herein, single particles of solid-state materials with core-shell structures were measured using on-line aerosol time-of-flight mass spectrometry (ATOFMS). Laser 'depth profiling' experiments verified the core-shell nature of two known core-shell particle configurations (< 2 mu m diameter) that possessed inverted, complimentary core-shell compositions (ZrO2@SiO2 versus SiO2@ZrO2). The average peak area ratios of Si and Zr ions were calculated to definitively show their core-shell composition. These ratio curves acted as a calibrant for anmore » uncharacterized sample - a metal-organic framework (MOF) material surround by silica (UiO-66(Zr)@SiO2; UiO = University of Oslo). ATOFMS depth profiling was used to show that these particles did indeed exhibit a core-shell architecture. The results presented here show that ATOFMS can provide unique insights into core-shell solid-state materials with particle diameters between 0.2-3 mu m.« less

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.

Uranium in larval shells as a barometer of molluscan ocean acidification exposure.

PubMed

Frieder, Christina A; Gonzalez, Jennifer P; Levin, Lisa A

2014-06-03

As the ocean undergoes acidification, marine organisms will become increasingly exposed to reduced pH, yet variability in many coastal settings complicates our ability to accurately estimate pH exposure for those organisms that are difficult to track. Here we present shell-based geochemical proxies that reflect pH exposure from laboratory and field settings in larvae of the mussels Mytilus californianus and M. galloprovincialis. Laboratory-based proxies were generated from shells precipitated at pH 7.51 to 8.04. U/Ca, Sr/Ca, and multielemental signatures represented as principal components varied with pH for both species. Of these, U/Ca was the best predictor of pH and did not vary with larval size, with semidiurnal pH fluctuations, or with oxygen concentration. Field applications of U/Ca were tested with mussel larvae reared in situ at both known and unknown pH conditions. Larval shells precipitated in a region of greater upwelling had higher U/Ca, and these U/Ca values corresponded well with the laboratory-derived U/Ca-pH proxy. Retention of the larval shell after settlement in molluscs allows use of this geochemical proxy to assess ocean acidification effects on marine populations.

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

Fate and effects of 2,4,6-trinitrotoluene (TNT) from dumped ammunition in a field study with fish and invertebrates.

PubMed

Ek, Helene; Dave, Göran; Nilsson, Eva; Sturve, Joachim; Birgersson, Göran

2006-08-01

2,4,6-Trinitrotoluene (TNT) is the major explosive ingredient in ammunition dumped into lakes and sea after World War II. The aim of the present field study was to study the fate and effect of TNT and its degradation products from dumped ammunition. Artillery shells were cleaved longitudinally to expose TNT and placed in open boxes filled with sediment, and then placed at the sea bottom. Sediment samples were taken in each box at the start and after 3, 9, 13, 20, 24, 33, and 36 months, and the sediments were tested for toxicity with bioassays using Nitocra spinipes (96 h), Hyalella azteca (96 h), and Daphnia magna (24 and 48 h). The result from the bioassays showed no impact of dumped ammunition on the survival of H. azteca and mobility of D. magna. Bioassays with N. spinipes showed significant differences in toxicity between control boxes and boxes with shells after 9 months and thereafter. The mean mortality (+/- SD) of N. spinipes in boxes with shells was 63 +/- 22%, and the mortality in control boxes was 23 +/- 17%. No continuous increase in sediment toxicity over time was found. After 3 years, cages with European flounder (Platichtys flesus) and blue mussels (Mytilus edulis) were attached to the boxes. The fish were examined for biochemical and physiological effects 8 weeks later. Exposure to ammunition, which had rested on the sea bottom 3 years, caused no significant effects on body indices, hematological variables, and detoxification and antioxidant enzymes activities in the flounder. The sediment, bile, and blood plasma of exposed fish, and hepatopancreas of exposed mussels, contained no detectable levels of TNT and its metabolites. Only minor disappearance of TNT from the shells could be detected by visual inspection on site (by scuba divers). This study suggests that the survival of sensitive benthic organisms, e.g., N. spinipes, might be negatively affected at an ammunition dumping site.

How effective is intermittent chlorination to control adult mussel fouling in cooling water systems?

PubMed

Rajagopal, Sanjeevi; Van der Velde, Gerard; Van der Gaag, Marinus; Jenner, Henk A

2003-01-01

Mussel control in cooling water systems is generally achieved by means of chlorination. Chlorine is applied continuously or intermittently, depending on cost and discharge criteria. In this paper, we examined whether mussels will be able to survive intermittent chlorination because of their ability to close their valves during periods of chlorination. Experiments were carried out using three common species of mussels: a freshwater mussel, Dreissena polymorpha, a brackish water mussel, Mytilopsis leucophaeata and a marine mussel, Mytilus edulis. The mussels were subjected to continuous or intermittent (4 h chlorination followed by 4 h no chlorination) chlorination at concentrations varying from 1 to 3 mg l(-1) and their responses (lethal and sublethal) were compared to those of control mussels. In addition, shell valve activity of mussels was monitored using a Mussel-monitor. Data clearly indicate that mussels shut their valves as soon as chlorine is detected in the environment and open only after chlorine dosing is stopped. However, under continuous chlorination mussels are constrained to keep the shell valves shut continuously. The mussels subjected to continuous chlorination at 1 mg l(-1) showed 100% mortality after 588 h (D. polymorpha), 966 h (Mytilus edulis) and 1104 h (Mytilopsis leucophaeata), while those subjected to intermittent chlorination at 1 mg l(-1) showed very little or no mortality during the same periods. Filtration rate, foot activity index and shell valve movement of D. polymorpha, Mytilopsis leucophaeata and Mytilus edulis decreased more than 90% at 1 mg l(-1) chlorine residual when compared to control. However, mussels subjected to intermittent chlorination showed a similar reduction (about 90%) in filtration rate, foot activity index and shell valve movement during chlorination and 3% during breaks in chlorination. The data indicate that intermittent chlorination between 1 and 3 mg l(-1) applied at 4 h on and 4 h off cycle is unlikely to control biofouling if mussels are the dominant fouling organisms.

Hierarchical inorganic-organic multi-shell nanospheres for intervention and treatment of lead-contaminated blood

NASA Astrophysics Data System (ADS)

Khairy, Mohamed; El-Safty, Sherif A.; Shenashen, Mohamed. A.; Elshehy, Emad A.

2013-08-01

The highly toxic properties, bioavailability, and adverse effects of Pb2+ species on the environment and living organisms necessitate periodic monitoring and removal whenever possible of Pb2+ concentrations in the environment. In this study, we designed a novel optical multi-shell nanosphere sensor that enables selective recognition, unrestrained accessibility, continuous monitoring, and efficient removal (on the order of minutes) of Pb2+ ions from water and human blood, i.e., red blood cells (RBCs). The consequent decoration of the mesoporous core/double-shell silica nanospheres through a chemically responsive azo-chromophore with a long hydrophobic tail enabled us to create a unique hierarchical multi-shell sensor. We examined the efficiency of the multi-shell sensor in removing lead ions from the blood to ascertain the potential use of the sensor in medical applications. The lead-induced hemolysis of RBCs in the sensing/capture assay was inhibited by the ability of the hierarchical sensor to remove lead ions from blood. The results suggest the higher flux and diffusion of Pb2+ ions into the mesopores of the core/multi-shell sensor than into the RBC membranes. These findings indicate that the sensor could be used in the prevention of health risks associated with elevated blood lead levels such as anemia.The highly toxic properties, bioavailability, and adverse effects of Pb2+ species on the environment and living organisms necessitate periodic monitoring and removal whenever possible of Pb2+ concentrations in the environment. In this study, we designed a novel optical multi-shell nanosphere sensor that enables selective recognition, unrestrained accessibility, continuous monitoring, and efficient removal (on the order of minutes) of Pb2+ ions from water and human blood, i.e., red blood cells (RBCs). The consequent decoration of the mesoporous core/double-shell silica nanospheres through a chemically responsive azo-chromophore with a long hydrophobic tail enabled us to create a unique hierarchical multi-shell sensor. We examined the efficiency of the multi-shell sensor in removing lead ions from the blood to ascertain the potential use of the sensor in medical applications. The lead-induced hemolysis of RBCs in the sensing/capture assay was inhibited by the ability of the hierarchical sensor to remove lead ions from blood. The results suggest the higher flux and diffusion of Pb2+ ions into the mesopores of the core/multi-shell sensor than into the RBC membranes. These findings indicate that the sensor could be used in the prevention of health risks associated with elevated blood lead levels such as anemia. Electronic supplementary information (ESI) available: The experimental procedures for synthesis of AC-LHT, mesoporous core/double shell silica, and optical core/multi-shell sensors. The adsorption capacity, optical recognition of Pb ions, colorimetric response of Pb ions in ethanol medium, Langmuir adsorption isotherm and reusability of captor are addressed. See DOI: 10.1039/c3nr02403b

Characterization of the multilayered shell of a limpet, Lottia kogamogai (Mollusca: Patellogastropoda), using SEM-EBSD and FIB-TEM techniques.

PubMed

Suzuki, Michio; Kameda, Jun; Sasaki, Takenori; Saruwatari, Kazuko; Nagasawa, Hiromichi; Kogure, Toshihiro

2010-08-01

The microstructure and its crystallographic aspect of the shell of a limpet, Lottiakogamogai, have been investigated, as the first step to clarify the mechanism of shell formation in limpet. The shell consists of five distinct layers stacked along the shell thickness direction. Transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique was primarily adopted, as well as scanning electron microscopy (SEM) with electron back-scattered diffraction (EBSD). The five layers were termed as M+3, M+2, M+1, M, M-1 from the outside to the inside in previous works, where M means myostracum. The outmost M+3 layer consists of calcite with a "mosaic" structure; granular submicron sub-grains with small-angle grain boundaries often accompanying dislocation arrays. M+2 layer consists of flat prismatic aragonite crystals with a leaf-like cross section, stacked obliquely to the shell surface. It looks that the prismatic crystals are surrounded by organic sheets, forming a compartment structure. M+1 and M-1 layers adopt a crossed lamellar structure consisting of aragonite flat prisms with rectangular cross section. M layer has a prismatic structure of aragonite perpendicular to the shell surface and with irregular shaped cross sections. Distinct organic sheets were not observed between the crystals in M+1, M and M-1 layers. The {110} twins are common in all aragonite M+2, M+1, M and M-1 layers, with the twin boundaries parallel to the prisms. These results for the microstructure of each layer should be considered in the discussion of the formation mechanism of the limpet shell structure. Copyright 2010 Elsevier Inc. All rights reserved.

Microstructure and Thermal Reliability of Microcapsules Containing Phase Change Material with Self-Assembled Graphene/Organic Nano-Hybrid Shells.

PubMed

Wang, Xianfeng; Guo, Yandong; Su, Junfeng; Zhang, Xiaolong; Han, Ningxu; Wang, Xinyu

2018-05-24

In recent decades, microcapsules containing phase change materials (microPCMs) have been the center of much attention in the field of latent thermal energy storage. The aim of this work was to prepare and investigate the microstructure and thermal conductivity of microPCMs containing self-assembled graphene/organic hybrid shells. Paraffin was used as a phase change material, which was successfully microencapsulated by graphene and polymer forming hybrid composite shells. The physicochemical characters of microPCM samples were investigated including mean size, shell thickness, and chemical structure. Scanning electron microscope (SEM) results showed that the microPCMs were spherical particles and graphene enhanced the degree of smoothness of the shell surface. The existence of graphene in the shells was proved by using the methods of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). It was found that graphene hybrid shells were constructed by forces of electric charge absorption and long-molecular entanglement. MicroPCMs with graphene had a higher degradation temperature of 300 °C. Graphene greatly enhanced the thermal stability of microPCMs. The thermal conductivity tests indicated that the phase change temperature of microPCMs was regulated by the graphene additive because of enhancement of the thermal barrier of the hybrid shells. Differential scanning calorimetry (DSC) tests proved that the latent thermal energy capability of microPCMs had been improved with a higher heat conduction rate. In addition, infrared thermograph observations implied that the microPCMs had a sensitivity response to heat during the phase change cycling process because of the excellent thermal conductivity of graphene.

Mechanisms to Explain the Elemental Composition of the Initial Aragonite Shell of Larval Oysters

NASA Astrophysics Data System (ADS)

Haley, Brian A.; Hales, Burke; Brunner, Elizabeth L.; Kovalchik, Kevin; Waldbusser, George G.

2018-04-01

Calcifying organisms face increasing stress from the changing carbonate chemistry of an acidifying ocean, particularly bivalve larvae that live in upwelling regions of the world, such as the coastal and estuarine waters of Oregon (USA). Arguably the first and most significant developmental hurdle faced by larval oysters is formation of their initial prodissoconch I (PDI) shell, upon which further ontological development depends. We measured the minor metal compositions (Sr/Ca, Mg/Ca) of this aragonitic PDI shell and of post-PDI larval Crassostrea gigas shell, as well as the water they were reared in, over ˜20 days for a May and an August cohort in 2011, during which time there was no period of carbonate under-saturation. After testing various methods, we successfully isolated the shell from organic tissue using a 5% active chlorine bleach solution. Elemental compositions (Sr, Mg, C, N) of the shells post-treatment showed that shell Sr/Ca ranged from 1.55 to 1.82 mmol/mol; Mg/Ca from 0.60 to 1.11 mmol/mol, similar to the few comparable published data for larval oyster aragonite compositions. We compare these data in light of possible biomineralization mechanisms: an amorphous calcium carbonate (ACC) path, an intercellular path, and a direct-from-seawater path to shell formation via biologically induced inorganic precipitation of aragonite. The last option provides a mechanistic explanation for: (1) the accelerated precipitation rates of biogenic calcification in the absence of a calcifying fluid; (2) consistently elevated precipitation rates at varying ambient-water saturation states; and (3) the high Ca-selectivity of the early larval calcification despite rapid precipitation rates.

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.

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

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.

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.

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.

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.

Synthesis of carbon core–shell pore structures and their performance as supercapacitors

DOE PAGES

Ariyanto, Teguh; Dyatkin, Boris; Zhang, Gui-Rong; ...

2015-07-15

High-power supercapacitors require excellent electrolyte mobility within the pore network and high electrical conductivity for maximum capacitance and efficiency. Achieving high power typically requires sacrificing energy densities, as the latter demands a high specific surface area and narrow porosity that impedes ion transport. Here, we present a novel solution for this optimization problem: a nanostructured core–shell carbonaceous material that exhibits a microporous carbon core surrounded by a mesoporous, graphitic shell. The tunable synthesis parameters yielded a structure that features either a sharp or a gradual transition between the core and shell sections. Electrochemical supercapacitor testing using organic electrolyte revealed thatmore » these novel core–shell materials outperform carbons with homogeneous pore structures. The hybrid core–shell materials showed a combination of good capacitance retention, typical for the carbon present in the shell and high specific capacitance, typical for the core material. These materials achieved power densities in excess of 40 kW kg -1 at energy densities reaching 27 Wh kg -1.« less

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.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzmán, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2009-02-01

Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzman, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2008-02-01

Variations on chemical composition in fossil biogenic carbonates, and in particular of mollusk shells, have been used in a range of palaeoenvironmental reconstructions. Therefore, it is of primary importance to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Pleistocene and Holocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusk shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to attest shell sample conservation state should not be considered as sufficient.

Monolithic photonic crystals created by partial coalescence of core-shell particles.

PubMed

Lee, Joon-Seok; Lim, Che Ho; Yang, Seung-Man; Kim, Shin-Hyun

2014-03-11

Colloidal crystals and their derivatives have been intensively studied and developed during the past two decades due to their unique photonic band gap properties. However, complex fabrication procedures and low mechanical stability severely limit their practical uses. Here, we report stable photonic structures created by using colloidal building blocks composed of an inorganic core and an organic shell. The core-shell particles are convectively assembled into an opal structure, which is then subjected to thermal annealing. During the heat treatment, the inorganic cores, which are insensitive to heat, retain their regular arrangement in a face-centered cubic lattice, while the organic shells are partially fused with their neighbors; this forms a monolithic structure with high mechanical stability. The interparticle distance and therefore stop band position are precisely controlled by the annealing time; the distance decreases and the stop band blue shifts during the annealing. The composite films can be further treated to give a high contrast in the refractive index. The inorganic cores are selectively removed from the composite by wet etching, thereby providing an organic film containing regular arrays of air cavities. The high refractive index contrast of the porous structure gives rise to pronounced structural colors and high reflectivity at the stop band position.

Novel Organically Modified Core-Shell Clay for Epoxy Composites-"SOBM Filler 1".

PubMed

Iheaturu, Nnamdi Chibuike; Madufor, Innocent Chimezie

2014-01-01

Preparation of a novel organically modified clay from spent oil base drilling mud (SOBM) that could serve as core-shell clay filler for polymers is herein reported. Due to the hydrophilic nature of clay, its compatibility with polymer matrix was made possible through modification of the surface of the core clay sample with 3-aminopropyltriethoxysilane (3-APTES) compound prior to its use. Fourier transform infrared (FT-IR) spectroscopy was used to characterize clay surface modification. Electron dispersive X-ray diffraction (EDX) and scanning electron microscopy (SEM) were used to expose filler chemical composition and morphology, while electrophoresis measurement was used to examine level of filler dispersion. Results show an agglomerated core clay powder after high temperature treatment, while EDX analysis shows that the organically modified clay is composed of chemical inhomogeneities, wherein elemental compositions in weight percent vary from one point to the other in a probe of two points. Micrographs of the 3-APTES coupled SOBM core-shell clay filler clearly show cloudy appearance, while FT-IR indicates 25% and 5% increases in fundamental vibrations band at 1014 cm(-1) and 1435 cm(-1), respectively. Furthermore, 3-APTES coupled core-shell clay was used to prepare epoxy composites and tested for mechanical properties.

Role of reef fauna in sediment transport and distribution - Studies from Tektite I and II

USGS Publications Warehouse

Clifton, H.E.

1973-01-01

1. Reef organisms may play a major role in the transport and distribution of sediment on the sea floor adjacent to coral reefs. 2. Some fish such as Malacanthus plumieri (Bloch) selectively transport and collect certain types of sediment (such as larger coral and shell fragments). 3. The random movement of crawling or burrowing organisms may cause a large amount of sediment to be shifted laterally on the sea floor. On slopes, a net downhill displacement may result. 4. The surface configuration and internal structure of the sediment is rapidly changed by faunal mixing. Ripple marks formed by waves or currents are obliterated by the activity of organisms in only a few weeks in the environment studied. Internal structure (bedding) near the sediment-water interface is similarly destroyed in a short period of time. 5. Larger clasts (including empty shells) on the sea floor tend to be buried by faunal undermining. The rate of burial depends primarily on the grain size of the substrate. 6. The random movement of fauna on the sea floor may produce a predominantly concave-up orientation of pelecypod shells and shell fragments on the sea floor - the opposite of that produced by the activity of waves or currents. ?? 1973 Biologischen Anstalt Helgoland.

Novel Organically Modified Core-Shell Clay for Epoxy Composites—“SOBM Filler 1”

PubMed Central

Iheaturu, Nnamdi Chibuike; Madufor, Innocent Chimezie

2014-01-01

Preparation of a novel organically modified clay from spent oil base drilling mud (SOBM) that could serve as core-shell clay filler for polymers is herein reported. Due to the hydrophilic nature of clay, its compatibility with polymer matrix was made possible through modification of the surface of the core clay sample with 3-aminopropyltriethoxysilane (3-APTES) compound prior to its use. Fourier transform infrared (FT-IR) spectroscopy was used to characterize clay surface modification. Electron dispersive X-ray diffraction (EDX) and scanning electron microscopy (SEM) were used to expose filler chemical composition and morphology, while electrophoresis measurement was used to examine level of filler dispersion. Results show an agglomerated core clay powder after high temperature treatment, while EDX analysis shows that the organically modified clay is composed of chemical inhomogeneities, wherein elemental compositions in weight percent vary from one point to the other in a probe of two points. Micrographs of the 3-APTES coupled SOBM core-shell clay filler clearly show cloudy appearance, while FT-IR indicates 25% and 5% increases in fundamental vibrations band at 1014 cm−1 and 1435 cm−1, respectively. Furthermore, 3-APTES coupled core-shell clay was used to prepare epoxy composites and tested for mechanical properties. PMID:27355022

In-depth proteomic analysis of shell matrix proteins of Pinctada fucata

PubMed Central

Liu, Chuang; Li, Shiguo; Kong, Jingjing; Liu, Yangjia; Wang, Tianpeng; Xie, Liping; Zhang, Rongqing

2015-01-01

The shells of pearl oysters, Pinctada fucata, are composed of calcite and aragonite and possess remarkable mechanical properties. These shells are formed under the regulation of macromolecules, especially shell matrix proteins (SMPs). Identification of diverse SMPs will lay a foundation for understanding biomineralization process. Here, we identified 72 unique SMPs using liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis of proteins extracted from the shells of P. fucata combined with a draft genome. Of 72 SMPs, 17 SMPs are related to both the prismatic and nacreous layers. Moreover, according to the diverse domains found in the SMPs, we hypothesize that in addition to controlling CaCO3 crystallization and crystal organization, these proteins may potentially regulate the extracellular microenvironment and communicate between cells and the extracellular matrix (ECM). Immunohistological localization techniques identify the SMPs in the mantle, shells and synthetic calcite. Together, these proteomic data increase the repertoires of the shell matrix proteins in P. fucata and suggest that shell formation in P. fucata may involve tight regulation of cellular activities and the extracellular microenvironment. PMID:26608573

Band engineered epitaxial 3D GaN-InGaN core-shell rod arrays as an advanced photoanode for visible-light-driven water splitting.

PubMed

Caccamo, Lorenzo; Hartmann, Jana; Fàbrega, Cristian; Estradé, Sonia; Lilienkamp, Gerhard; Prades, Joan Daniel; Hoffmann, Martin W G; Ledig, Johannes; Wagner, Alexander; Wang, Xue; Lopez-Conesa, Lluis; Peiró, Francesca; Rebled, José Manuel; Wehmann, Hergo-Heinrich; Daum, Winfried; Shen, Hao; Waag, Andreas

2014-02-26

3D single-crystalline, well-aligned GaN-InGaN rod arrays are fabricated by selective area growth (SAG) metal-organic vapor phase epitaxy (MOVPE) for visible-light water splitting. Epitaxial InGaN layer grows successfully on 3D GaN rods to minimize defects within the GaN-InGaN heterojunctions. The indium concentration (In ∼ 0.30 ± 0.04) is rather homogeneous in InGaN shells along the radial and longitudinal directions. The growing strategy allows us to tune the band gap of the InGaN layer in order to match the visible absorption with the solar spectrum as well as to align the semiconductor bands close to the water redox potentials to achieve high efficiency. The relation between structure, surface, and photoelectrochemical property of GaN-InGaN is explored by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), Auger electron spectroscopy (AES), current-voltage, and open circuit potential (OCP) measurements. The epitaxial GaN-InGaN interface, pseudomorphic InGaN thin films, homogeneous and suitable indium concentration and defined surface orientation are properties demanded for systematic study and efficient photoanodes based on III-nitride heterojunctions.

Enterobacteriaceae and related organisms recovered from biofilms in a commercial shell egg processing facility.

USDA-ARS?s Scientific Manuscript database

During six visits, biofilms from egg contact and non-contact surfaces in a commercial shell egg processing facility were sampled. Thirty-five different sample sites were selected: Pre-wash and wash tanks (lids, screens, tank interiors, nozzle guards), post-wash spindles, blower filters, belts (far...

Comparison of Mediterranean Pteropod Shell Biometrics and Ultrastructure from Historical (1910 and 1921) and Present Day (2012) Samples Provides Baseline for Monitoring Effects of Global Change.

PubMed

Howes, Ella L; Eagle, Robert A; Gattuso, Jean-Pierre; Bijma, Jelle

2017-01-01

Anthropogenic carbon perturbation has caused decreases in seawater pH and increases in global temperatures since the start of the 20th century. The subsequent lowering of the saturation state of CaCO3 may make the secretion of skeletons more problematic for marine calcifiers. As organisms that precipitate thin aragonite shells, thecosome pteropods have been identified as being particularly vulnerable to climate change effects. Coupled with their global distribution, this makes them ideal for use as sentinel organisms. Recent studies have highlighted shell dissolution as a potential indicator of ocean acidification; however, this metric is not applicable for monitoring pH changes in supersaturated basins. In this study, the novel approach of high resolution computed tomography (CT) scanning was used to produce quantitative 3-dimensional renderings pteropod shells to assess the potential of using this method to monitor small changes in shell biometrics that may be driven by climate change drivers. An ontogenetic analysis of the shells of Cavolinia inflexa and Styliola subula collected from the Mediterranean was used to identify suitable monitoring metrics. Modern samples were then compared to historical samples of the same species, collected during the Mediterranean leg of the Thor (1910) and Dana (1921) cruises to assess whether any empirical differences could be detected. Shell densities were calculated and scanning electron microscopy was used to compare the aragonite crystal morphology. pH for the collection years was hind-cast using temperature and salinity time series with atmospheric CO2 concentrations from ice core data. Historical samples of S. subula were thicker than S. subula shells of the same size from 2012 and C. inflexa shells collected in 1910 were significantly denser than those from 2012. These results provide a baseline for future work to develop monitoring techniques for climate change in the oceans using the novel approach of high-resolution CT scanning.

Comparison of Mediterranean Pteropod Shell Biometrics and Ultrastructure from Historical (1910 and 1921) and Present Day (2012) Samples Provides Baseline for Monitoring Effects of Global Change

PubMed Central

Gattuso, Jean-Pierre; Bijma, Jelle

2017-01-01

Anthropogenic carbon perturbation has caused decreases in seawater pH and increases in global temperatures since the start of the 20th century. The subsequent lowering of the saturation state of CaCO3 may make the secretion of skeletons more problematic for marine calcifiers. As organisms that precipitate thin aragonite shells, thecosome pteropods have been identified as being particularly vulnerable to climate change effects. Coupled with their global distribution, this makes them ideal for use as sentinel organisms. Recent studies have highlighted shell dissolution as a potential indicator of ocean acidification; however, this metric is not applicable for monitoring pH changes in supersaturated basins. In this study, the novel approach of high resolution computed tomography (CT) scanning was used to produce quantitative 3-dimensional renderings pteropod shells to assess the potential of using this method to monitor small changes in shell biometrics that may be driven by climate change drivers. An ontogenetic analysis of the shells of Cavolinia inflexa and Styliola subula collected from the Mediterranean was used to identify suitable monitoring metrics. Modern samples were then compared to historical samples of the same species, collected during the Mediterranean leg of the Thor (1910) and Dana (1921) cruises to assess whether any empirical differences could be detected. Shell densities were calculated and scanning electron microscopy was used to compare the aragonite crystal morphology. pH for the collection years was hind-cast using temperature and salinity time series with atmospheric CO2 concentrations from ice core data. Historical samples of S. subula were thicker than S. subula shells of the same size from 2012 and C. inflexa shells collected in 1910 were significantly denser than those from 2012. These results provide a baseline for future work to develop monitoring techniques for climate change in the oceans using the novel approach of high-resolution CT scanning. PMID:28125590

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.

The role of home-made ice cream as a vehicle of Salmonella enteritidis phage type 4 infection from fresh shell eggs.

PubMed Central

Morgan, D.; Mawer, S. L.; Harman, P. L.

1994-01-01

A family outbreak of Salmonella enteritidis PT4 infection is described in which home-made ice cream was identified as the vehicle of infection. The ice cream contained approximately 10(5) S. enteritidis PT4 organisms per gm and was probably contaminated by an infected shell egg containing between 10(5)-10(8) organisms. The continued relevance of the Chief Medical Officer's warning on the use of raw shell eggs is highlighted. Home-made ice cream using the same recipe as ice cream that had been incriminated as the cause of the family outbreak of S. enteritidis PT4 infection was used to study the growth of the organism that might have occurred in the 3-4 h it took to prepare the product. When the inoculum was in the stationary phase, as it would be from shell or other cross contamination, there was a lag phase of 3 h before growth occurred at room temperature. Even when actively multiplying organisms were introduced, as may be found in an infected egg, there was less than 3 log(10) increase in the salmonella count in 4 h at room temperature. It was, therefore, given the high S. enteritidis count, unlikely that the ice cream was cross-contaminated. By contrast, raspberry sorbet at pH 3.73 proved to be lethal to a large inoculum of S. enteritidis and may be a relatively safe raw egg containing product. PMID:8062876

Removal of Volatile Organics from Humidified Air Streams by Absorption.

DTIC Science & Technology

1987-12-01

Type Comments Activated Carbons: SK-4 nut shell LCL coconut shell WV-B coal base CT coconut shell Specialty Carbons: Graphpac graphitized carbon area...Capacity, g/g Percentage Sorbent ( virgin ) (treated)D Change SK-4 0.114 0.117 +2.6 Carbosieve S-11 0.195 0.180 -7.7 Spherocarb 0.149 0.151 +1.3 CT...and WV-B with respect to their adsorption capacities. CT and SK-4 are both coconut -derived carbons produced by the same manufacturer. Differences

Volume-labeled nanoparticles and methods of preparation

DOEpatents

Wang, Wei; Gu, Baohua; Retterer, Scott T; Doktycz, Mitchel J

2015-04-21

Compositions comprising nanosized objects (i.e., nanoparticles) in which at least one observable marker, such as a radioisotope or fluorophore, is incorporated within the nanosized object. The nanosized objects include, for example, metal or semi-metal oxide (e.g., silica), quantum dot, noble metal, magnetic metal oxide, organic polymer, metal salt, and core-shell nanoparticles, wherein the label is incorporated within the nanoparticle or selectively in a metal oxide shell of a core-shell nanoparticle. Methods of preparing the volume-labeled nanoparticles are also described.

Layer-by-layer-based silica encapsulation of individual yeast with thickness control.

PubMed

Lee, Hojae; Hong, Daewha; Choi, Ji Yu; Kim, Ji Yup; Lee, Sang Hee; Kim, Ho Min; Yang, Sung Ho; Choi, Insung S

2015-01-01

In the area of cell-surface engineering with nanomaterials, the metabolic and functional activities of the encapsulated cells are manipulated and controlled by various parameters of the artificial shells that encase the cells, such as stiffness and elasticity, thickness, and porosity. The mechanical durability and physicochemical stability of inorganic shells prove superior to layer-by-layer-based organic shells with regard to cytoprotection, but it has been difficult to vary the parameters of inorganic shells including their thickness. In this work, we combine the layer-by-layer technique with a process of bioinspired silicification to control the thickness of the silica shells that encapsulate yeast Saccharomyces cerevisiae cells individually, and investigate the thickness-dependent microbial growth. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Environmental salinity modulates the effects of elevated CO2 levels on juvenile hard-shell clams, Mercenaria mercenaria.

PubMed

Dickinson, Gary H; Matoo, Omera B; Tourek, Robert T; Sokolova, Inna M; Beniash, Elia

2013-07-15

Ocean acidification due to increasing atmospheric CO2 concentrations results in a decrease in seawater pH and shifts in the carbonate chemistry that can negatively affect marine organisms. Marine bivalves such as the hard-shell clam, Mercenaria mercenaria, serve as ecosystem engineers in estuaries and coastal zones of the western Atlantic and, as for many marine calcifiers, are sensitive to the impacts of ocean acidification. In estuaries, the effects of ocean acidification can be exacerbated by low buffering capacity of brackish waters, acidic inputs from freshwaters and land, and/or the negative effects of salinity on the physiology of organisms. We determined the interactive effects of 21 weeks of exposure to different levels of CO2 (~395, 800 and 1500 μatm corresponding to pH of 8.2, 8.1 and 7.7, respectively) and salinity (32 versus 16) on biomineralization, shell properties and energy metabolism of juvenile hard-shell clams. Low salinity had profound effects on survival, energy metabolism and biomineralization of hard-shell clams and modulated their responses to elevated PCO2. Negative effects of low salinity in juvenile clams were mostly due to the strongly elevated basal energy demand, indicating energy deficiency, that led to reduced growth, elevated mortality and impaired shell maintenance (evidenced by the extensive damage to the periostracum). The effects of elevated PCO2 on physiology and biomineralization of hard-shell clams were more complex. Elevated PCO2 (~800-1500 μatm) had no significant effects on standard metabolic rates (indicative of the basal energy demand), but affected growth and shell mechanical properties in juvenile clams. Moderate hypercapnia (~800 μatm PCO2) increased shell and tissue growth and reduced mortality of juvenile clams in high salinity exposures; however, these effects were abolished under the low salinity conditions or at high PCO2 (~1500 μatm). Mechanical properties of the shell (measured as microhardness and fracture toughness of the shells) were negatively affected by elevated CO2 alone or in combination with low salinity, which may have important implications for protection against predators or environmental stressors. Our data indicate that environmental salinity can strongly modulate responses to ocean acidification in hard-shell clams and thus should be taken into account when predicting the effects of ocean acidification on estuarine bivalves.

Comparative study of the shell development of hard- and soft-shelled turtles

PubMed Central

Nagashima, Hiroshi; Shibata, Masahiro; Taniguchi, Mari; Ueno, Shintaro; Kamezaki, Naoki; Sato, Noboru

2014-01-01

The turtle shell provides a fascinating model for the investigation of the evolutionary modifications of developmental mechanisms. Different conclusions have been put forth for its development, and it is suggested that one of the causes of the disagreement could be the differences in the species of the turtles used – the differences between hard-shelled turtles and soft-shelled turtles. To elucidate the cause of the difference, we compared the turtle shell development in the two groups of turtle. In the dorsal shell development, these two turtle groups shared the gene expression profile that is required for formation, and shared similar spatial organization of the anatomical elements during development. Thus, both turtles formed the dorsal shell through a folding of the lateral body wall, and the Wnt signaling pathway appears to have been involved in the development. The ventral portion of the shell, on the other hand, contains massive dermal bones. Although expression of HNK-1 epitope has suggested that the trunk neural crest contributed to the dermal bones in the hard-shelled turtles, it was not expressed in the initial anlage of the skeletons in either of the types of turtle. Hence, no evidence was found that would support a neural crest origin. PMID:24754673

Comparative study of the shell development of hard- and soft-shelled turtles.

PubMed

Nagashima, Hiroshi; Shibata, Masahiro; Taniguchi, Mari; Ueno, Shintaro; Kamezaki, Naoki; Sato, Noboru

2014-07-01

The turtle shell provides a fascinating model for the investigation of the evolutionary modifications of developmental mechanisms. Different conclusions have been put forth for its development, and it is suggested that one of the causes of the disagreement could be the differences in the species of the turtles used - the differences between hard-shelled turtles and soft-shelled turtles. To elucidate the cause of the difference, we compared the turtle shell development in the two groups of turtle. In the dorsal shell development, these two turtle groups shared the gene expression profile that is required for formation, and shared similar spatial organization of the anatomical elements during development. Thus, both turtles formed the dorsal shell through a folding of the lateral body wall, and the Wnt signaling pathway appears to have been involved in the development. The ventral portion of the shell, on the other hand, contains massive dermal bones. Although expression of HNK-1 epitope has suggested that the trunk neural crest contributed to the dermal bones in the hard-shelled turtles, it was not expressed in the initial anlage of the skeletons in either of the types of turtle. Hence, no evidence was found that would support a neural crest origin. © 2014 Anatomical Society.

Relating Structure to Efficiency in Surfactant-Free Polymer/Fullerene Nanoparticle-Based Organic Solar Cells.

PubMed

Gärtner, Stefan; Clulow, Andrew J; Howard, Ian A; Gilbert, Elliot P; Burn, Paul L; Gentle, Ian R; Colsmann, Alexander

2017-12-13

Nanoparticle dispersions open up an ecofriendly route toward printable organic solar cells. They can be formed from a variety of organic semiconductors by using miniemulsions that employ surfactants to stabilize the nanoparticles in dispersion and to prevent aggregation. However, whenever surfactant-based nanoparticle dispersions have been used to fabricate solar cells, the reported performances remain moderate. In contrast, solar cells from nanoparticle dispersions formed by precipitation (without surfactants) can exhibit power conversion efficiencies close to those of state-of-the-art solar cells processed from blend solutions using chlorinated solvents. In this work, we use small-angle neutron scattering measurements and transient absorption spectroscopy to investigate why surfactant-free nanoparticles give rise to efficient organic solar cells. We show that surfactant-free nanoparticles comprise a uniform distribution of small semiconductor domains, similar to that of bulk-heterojunction films formed using traditional solvent processing. This observation differs from surfactant-based miniemulsion nanoparticles that typically exhibit core-shell structures. Hence, the surfactant-free nanoparticles already possess the optimum morphology for efficient energy conversion before they are assembled into the photoactive layer of a solar cell. This structural property underpins the superior performance of the solar cells containing surfactant-free nanoparticles and is an important design criterion for future nanoparticle inks.

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

The argonaut shell: gas-mediated buoyancy control in a pelagic octopus

PubMed Central

Finn, Julian K.; Norman, Mark D.

2010-01-01

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. PMID:20484241

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 Office of Scientific and Technical Information (OSTI.GOV)

Tian, Xinlong; Tang, Haibo; Luo, Junming

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

Retrospective environmental biomonitoring - Mussel Watch expanded

NASA Astrophysics Data System (ADS)

Schöne, Bernd R.; Krause, Richard A.

2016-09-01

Monitoring bioavailable contaminants and determining baseline conditions in aquatic environments has become an important aspect of ecology and ecotoxicology. Since the mid-1970s and the initiation of the Mussel Watch program, this has been successfully accomplished with bivalve mollusks. These (mostly) sessile organisms reliably and proportionately record changes of a range of organic and inorganic pollutants occurring in the water, food or sediment. The great majority of studies have measured the concentration of pollutants in soft tissues and, to a much lesser extent, in whole shells or fractions thereof. Both approaches come with several drawbacks. Neither soft tissues nor whole shells can resolve temporal changes of the pollution history, except through the analysis of multiple specimens collected at different times. Soft tissues and shell fractions provide time-averaged data spanning months or years, and whole shells time-averaged data over the entire lifespan of the animal. Even with regular sampling of multiple specimens over long intervals of time, the resulting chronology may not faithfully resolve short-term changes of water quality. Compounding the problem, whole shell averages tend to be non-arithmetic and non-linear, because shell growth rate varies through seasons and lifetime, and different shell layers often vary ultrastructurally and can thus be chemically different from each other. Mussel Watch could greatly benefit from the potential of bivalve shells in providing high-resolution, temporally aligned archives of environmental variability. So far, only circa a dozen studies have demonstrated that the sclerochronological approach - i.e., combined growth pattern and high-resolution chemical analyses - can provide sub-seasonally to annually resolved time-series documenting the history of pollution over centuries and even millennia. On the other hand, the sclerochronological community has failed to fully appreciate that the formation of the shell and its chemical composition is controlled by the soft parts and that a robust interpretation of the shell record requires a detailed understanding of bivalve physiology, behavior and ecology. This review attempts to bring together the Mussel Watch and sclerochronology communities and lay the foundation of a new subdiscipline of the Mussel Watch: retrospective environmental biomonitoring. For this purpose, we provide an overview of seminal work from both fields and outline potential future research directions.

Geochemical gradients within modern and fossil shells of Concholepas concholepas from northern Chile: an insight into U-Th systematics and diagenetic/authigenic isotopic imprints in mollusk shells

NASA Astrophysics Data System (ADS)

Labonne, Maylis; Hillaire-Marcel, Claude

2000-05-01

Seriate geochemical measurements through shells of one modern, one Holocene, and two Sangamonian Concholepas concholepas, from marine terraces of Northern Chile, were performed to document diagenetic vs. authigenic geochemical signatures, and to better interpret U-series ages on such material. Subsamples were recovered by drilling from the outer calcitic layer to the inner aragonitic layer of each of the studied shells. Unfortunately, this sampling procedure induces artifacts, notably the convertion of up to ˜20% of calcite into aragonite, and of up to ˜6% of aragonite into calcite, as well as in the epimerization of a few percent of isoleucine into D-alloisoleucine/ L-isoleucine. Negligible sampling artifacts were noticed for stable isotope and total amino acid contents. Diagenetic effects on the geochemical properties of the shells are particularly pronounced in the inner aragonitic layer and more discrete in the outer calcitic layer. The time-dependent decay of the organic matrix of the shell is illustrated by a one order of magnitude lower total amino acid content in the Sangamonian specimens by comparison with the modern shell. Conversely, the Sangamonian shells U contents increase by a similar factor and 13C- 18O enrichments as high as 2 to 3‰ seem also to occur through the same time interval possibly due to partial replacement of aragonite by gypsum. The decay of the organic matrix of the aragonitic layer of the shell is thought to play a major role with respect to U-uptake processes and stable isotope shifts. Nevertheless, asymptotic 230Th-ages (˜100 ka) in the inner U-rich layers of the Sangamonian shells, and 234U/ 238U ratios compatible with a marine origin for U, suggest U-uptake within a short diagenetic interval, when marine waters were still bathing the embedding sediment. Thus, U-series ages on fossil mollusks from such a hyper-arid environment should not differ much from the age of the corresponding marine unit deposition. However, the diagenetic enrichments in stable isotopes raise concerns about their use for paleoenvironmental reconstructions under such climate conditions.

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.

Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes.

PubMed

Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud

2017-03-15

For the first time the extract of the plant of Salvia hydrangea was used to green synthesis of Pd nanoparticles (NPs) supported on Apricot kernel shell as an environmentally benign support. The Pd NPs/Apricot kernel shell as an effective catalyst was prepared through reduction of Pd 2+ ions using Salvia hydrangea extract as the reducing and capping agent and Pd NPs immobilization on Apricot kernel shell surface in the absence of any stabilizer or surfactant. According to FT-IR analysis, the hydroxyl groups of phenolics in Salvia hydrangea extract as bioreductant agents are directly responsible for the reduction of Pd 2+ ions and formation of Pd NPs. The as-prepared catalyst was characterized by Fourier transform infrared (FT-IR) and UV-Vis spectroscopy, field emission scanning electron microscopy (FESEM) equipped with an energy dispersive X-ray spectroscopy (EDS), Elemental mapping, X-ray diffraction analysis (XRD) and transmittance electron microscopy (TEM). The synthesized catalyst was used in the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), Methylene Blue (MB), Rhodamine B (RhB), and Congo Red (CR) at room temperature. The Pd NPs/Apricot kernel shell showed excellent catalytic activity in the reduction of these organic dyes. In addition, it was found that Pd NPs/Apricot kernel shell can be recovered and reused several times without significant loss of catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

Interfacial redox reaction-directed synthesis of silver@cerium oxide core-shell nanocomposites as catalysts for rechargeable lithium-air batteries

NASA Astrophysics Data System (ADS)

Liu, Ying; Wang, Man; Cao, Lu-Jie; Yang, Ming-Yang; Ho-Sum Cheng, Samson; Cao, Chen-Wei; Leung, Kwan-Lan; Chung, Chi-Yuen; Lu, Zhou-Guang

2015-07-01

A facile oxidation-reduction reaction method has been implemented to prepare pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites. Under Ar atmosphere, redox reaction automatically occurs between AgNO3 and Ce(NO3)3 in an alkaline solution, where Ag+ is reduced to Ag nanopartilces and Ce3+ is simultaneously oxidized to form CeO2, followed by the self-assembly to form the pomegranate-like multicore-shell structured Ag@CeO2 nanocomposites driven by thermodynamic equilibrium. No other organic amines or surfactants are utilized in the whole reaction system and only NaOH instead of organic reducing agent is used to prevent the introduction of a secondary reducing byproduct. The as-obtained pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites have been characterized as electro-catalysts for the air cathode of lithium-air batteries operated in a simulated air environment. Superior electrochemical performance with high discharge capacity of 3415 mAh g-1 at 100 mA g-1, stable cycling and small charge/discharge polarization voltage is achieved, which is much better than that of the CeO2 or simple mixture of CeO2 and Ag. The enhanced properties can be primarily attributed to the synergy effect between the Ag core and the CeO2 shell resulting from the unique pomegranate-like multicore-shell nanostructures possessing plenty of active sites to promote the facile formation and decomposition of Li2O2.

Florida snapping turtle

NASA Image and Video Library

2007-10-22

A rare photo of a Florida snapping turtle out in the open on Beach Road, near NASA's Kennedy Space Center. Found only in Florida and Georgia, this species is related to the common snapping turtle. It is considered a dangerous turtle because it can snap very quickly with its extremely strong jaws. Its tail, which is almost as long as its shell, has saw-edges along the top. The shell also has rough points down the middle. The shell is tan to dark brown and may have green algae growing on it. It can grow to 17 inches long and weigh 45 pounds. Snapping turtles usually live in ponds under the shadows and don’t like to rest in the sun like most turtles. They eat almost anything: water bugs, fish, lizards, small birds, mice, plants and even dead animals.

Florida snapping turtle

NASA Image and Video Library

2007-10-22

A rare photo of a Florida snapping turtle out in the open on Beach Road, near NASA's Kennedy Space Center. Found only in Florida and Georgia, this species is related to the common snapping turtle. It is considered a dangerous turtle because it can snap very quickly with its extremely strong jaws. Its tail, which is almost as long as its shell, has saw-edges along the top. The shell also has rough points down the middle. The shell is tan to dark brown and may have green algae growing on it. It can grow to 17 inches long and weigh 45 pounds. Snapping turtles usually live in ponds under the shadows and don’t like to rest in the sun like most turtles. They eat almost anything: water bugs, fish, lizards, small birds, mice, plants and even dead animals

Experimental evaluation of drying characteristics of sewage sludge and hazelnut shell mixtures

NASA Astrophysics Data System (ADS)

Pehlivan, Hüseyin; Ateş, Asude; Özdemir, Mustafa

2016-11-01

In this study the drying behavior of organic and agricultural waste mixtures has been experimentally investigated. The usability of sewage sludge as an organic waste and hazelnut shell as an agricultural waste was assessed in different mixture range. The paper discusses the applicability of these mixtures as a recovery energy source. Moisture content of mixtures has been calculated in laboratory and plant conditions. Indoor and outdoor solar sludge drying plants were constructed in pilot scale for experimental purposes. Dry solids and climatic conditions were constantly measured. A total more than 140 samples including for drying has been carried out to build up results. Indoor and outdoor weather conditions are taken into consideration in winter and summer. The most effective drying capacity is obtained in mixture of 20 % hazelnut shell and 80 % sewage sludge.

Real-Time Intracellular Measurements of ROS and RNS in Living Cells with Single Core-Shell Nanowire Electrodes.

PubMed

Zhang, Xin-Wei; Qiu, Quan-Fa; Jiang, Hong; Zhang, Fu-Li; Liu, Yan-Lin; Amatore, Christian; Huang, Wei-Hua

2017-10-09

Nanoelectrodes allow precise and quantitative measurements of important biological processes at the single living-cell level in real time. Cylindrical nanowire electrodes (NWEs) required for intracellular measurements create a great challenge for achieving excellent electrochemical and mechanical performances. Herein, we present a facile and robust solution to this problem based on a unique SiC-core-shell design to produce cylindrical NWEs with superior mechanical toughness provided by the SiC nano-core and an excellent electrochemical performance provided by the ultrathin carbon shell that can be used as such or platinized. The use of such NWEs for biological applications is illustrated by the first quantitative measurements of ROS/RNS in individual phagolysosomes of living macrophages. As the shell material can be varied to meet any specific detection purpose, this work opens up new opportunities to monitor quantitatively biological functions occurring inside cells and their organelles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size-selective breaking of the core-shell structure of gallium nanoparticles.

PubMed

Catalán Gómez, Sergio; Redondo-Cubero, Andres; Palomares Simon, Francisco Javier; Vazquez Burgos, Luis; Nogales, Emilio; Nucciarelli, Flavio; Mendez, Bianchi; Gordillo, Nuria; Pau, Jose Luis

2018-06-11

Core-shell gallium nanoparticles (Ga NPs) have recently been proposed as an ultraviolet plasmonic material for different applications but only at room temperature. Here, the thermal stability as a function of the size of the NPs is reported over a wide range of temperatures. We analyse the chemical and structural properties of the oxide shell by x-ray photoelectron spectroscopy and atomic force microscopy. We demonstrate the inverse dependence of the shell breaking temperature with the size of the NPs. Spectroscopic ellipsometry is used for tracking the rupture and its mechanism is systematically investigated by scanning electron microscopy, grazing incidence x-ray diffraction and cathodoluminescence. Taking advantage of the thermal stability of the NPs, we perform complete oxidations that lead to homogenous gallium oxide NPs. Thus, this study set the physical limits of Ga NPs to last at high temperatures, and opens up the possibility to achieve totally oxidized NPs while keeping their sphericity. © 2018 IOP Publishing Ltd.

a-Si:H/SiNW shell/core for SiNW solar cell applications

PubMed Central

2013-01-01

Vertically aligned silicon nanowires have been synthesized by the chemical etching of silicon wafers. The influence of a hydrogenated amorphous silicon (a-Si:H) layer (shell) on top of a silicon nanowire (SiNW) solar cell has been investigated. The optical properties of a-Si:H/SiNWs and SiNWs are examined in terms of optical reflection and absorption properties. In the presence of the a-Si:H shell, 5.2% reflection ratio in the spectral range (250 to 1,000 nm) is achieved with a superior absorption property with an average over 87% of the incident light. In addition, the characteristics of the solar cell have been significantly improved, which exhibits higher open-circuit voltage, short-circuit current, and efficiency by more than 15%, 12%, and 37%, respectively, compared with planar SiNW solar cells. Based on the current–voltage measurements and morphology results, we show that the a-Si:H shell can passivate the defects generated by wet etching processes. PMID:24195734

Selection of pecan shell based activated carbons for removal of organic and inorganic impurities from simulated well-water

USDA-ARS?s Scientific Manuscript database

Activated carbons are a byproduct from pyrolysis and have value as a purifying agent. The effectiveness of activated carbons is dependent on feedstock selection and pyrolysis conditions that modify its surface properties. Therefore, pecan shell-based activated carbons (PSACs) were prepared by soakin...

Biological strategy for the fabrication of highly ordered aragonite helices: the microstructure of the cavolinioidean gastropods

PubMed Central

Checa, Antonio G.; Macías-Sánchez, Elena; Ramírez-Rico, Joaquín

2016-01-01

The Cavolinioidea are planktonic gastropods which construct their shells with the so-called aragonitic helical fibrous microstructure, consisting of a highly ordered arrangement of helically coiled interlocking continuous crystalline aragonite fibres. Our study reveals that, despite the high and continuous degree of interlocking between fibres, every fibre has a differentiated organic-rich thin external band, which is never invaded by neighbouring fibres. In this way, fibres avoid extinction. These intra-fibre organic-rich bands appear on the growth surface of the shell as minuscule elevations, which have to be secreted differentially by the outer mantle cells. We propose that, as the shell thickens during mineralization, fibre secretion proceeds by a mechanism of contact recognition and displacement of the tips along circular trajectories by the cells of the outer mantle surface. Given the sizes of the tips, this mechanism has to operate at the subcellular level. Accordingly, the fabrication of the helical microstructure is under strict biological control. This mechanism of fibre-by-fibre fabrication by the mantle cells is unlike that any other shell microstructure. PMID:27181457

Controllable Fabrication of Au Nanocups by Confined-Space Thermal Dewetting for OCT Imaging.

PubMed

Gao, Aiqin; Xu, Wenjing; Ponce de León, Yenisey; Bai, Yaocai; Gong, Mingfu; Xie, Kongliang; Park, Boris Hyle; Yin, Yadong

2017-07-01

Here, this study reports a novel confined-space thermal dewetting strategy for the fabrication of Au nanocups with tunable diameter, height, and size of cup opening. The nanocup morphology is defined by the cup-shaped void space created by a yolk-shell silica template that spontaneously takes an eccentric configuration during annealing. Thermal dewetting of Au, which is sandwiched between the yolk and shell, leads to the desired nanocup morphology. With strong scattering in near infrared, the Au nanocups exhibit superior efficiency as contrast agents for spectral-domain optical coherence tomography imaging. This confined-space thermal dewetting strategy is scalable and general, and can be potentially extended to the synthesis of novel anisotropic nanostructures of various compositions that are difficult to produce by conventional wet chemical or physical methods, thus opening up opportunities for many new applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum Chemistry on Quantum Computers: A Polynomial-Time Quantum Algorithm for Constructing the Wave Functions of Open-Shell Molecules.

PubMed

Sugisaki, Kenji; Yamamoto, Satoru; Nakazawa, Shigeaki; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Takui, Takeji

2016-08-18

Quantum computers are capable to efficiently perform full configuration interaction (FCI) calculations of atoms and molecules by using the quantum phase estimation (QPE) algorithm. Because the success probability of the QPE depends on the overlap between approximate and exact wave functions, efficient methods to prepare accurate initial guess wave functions enough to have sufficiently large overlap with the exact ones are highly desired. Here, we propose a quantum algorithm to construct the wave function consisting of one configuration state function, which is suitable for the initial guess wave function in QPE-based FCI calculations of open-shell molecules, based on the addition theorem of angular momentum. The proposed quantum algorithm enables us to prepare the wave function consisting of an exponential number of Slater determinants only by a polynomial number of quantum operations.

Electronic spectrum of the UO and UO(+) molecules.

PubMed

Tyagi, Rajni; Zhang, Zhiyong; Pitzer, Russell M

2014-12-18

Electronic theory calculations are applied to the study of the UO molecule and the UO(+) ion. Relativistic effective core potentials are used along with the accompanying valence spin-orbit operators. Polarized double-ς and triple-ς basis sets are used. Molecular orbitals are obtained from state-averaged multiconfiguration self-consistent field calculations and then used in multireference spin-orbit configuration interaction calculations with a number of millions of terms. The ground state of UO has open shells of 5f(3)7s(1), angular momentum Ω = 4, and a spin-orbit-induced avoided crossing near the equilibrium internuclear distance. Many UO excited states are studied with rotational constants, intensities, and experimental comparisons. The ground state of UO(+) is of 5f(3) nature with Ω = 9/2. Many UO(+) excited states are also studied. The open-shell nature of both UO and UO(+) leads to many low-lying excited states.

Porphyrin conjugated SiC/SiOx nanowires for X-ray-excited photodynamic therapy.

PubMed

Rossi, F; Bedogni, E; Bigi, F; Rimoldi, T; Cristofolini, L; Pinelli, S; Alinovi, R; Negri, M; Dhanabalan, S C; Attolini, G; Fabbri, F; Goldoni, M; Mutti, A; Benecchi, G; Ghetti, C; Iannotta, S; Salviati, G

2015-01-05

The development of innovative nanosystems opens new perspectives for multidisciplinary applications at the frontier between materials science and nanomedicine. Here we present a novel hybrid nanosystem based on cytocompatible inorganic SiC/SiOx core/shell nanowires conjugated via click-chemistry procedures with an organic photosensitizer, a tetracarboxyphenyl porphyrin derivative. We show that this nanosystem is an efficient source of singlet oxygen for cell oxidative stress when irradiated with 6 MV X-Rays at low doses (0.4-2 Gy). The in-vitro clonogenic survival assay on lung adenocarcinoma cells shows that 12 days after irradiation at a dose of 2 Gy, the cell population is reduced by about 75% with respect to control cells. These results demonstrate that our approach is very efficient to enhance radiation therapy effects for cancer treatments.

Porphyrin conjugated SiC/SiOx nanowires for X-ray-excited photodynamic therapy

NASA Astrophysics Data System (ADS)

Rossi, F.; Bedogni, E.; Bigi, F.; Rimoldi, T.; Cristofolini, L.; Pinelli, S.; Alinovi, R.; Negri, M.; Dhanabalan, S. C.; Attolini, G.; Fabbri, F.; Goldoni, M.; Mutti, A.; Benecchi, G.; Ghetti, C.; Iannotta, S.; Salviati, G.

2015-01-01

The development of innovative nanosystems opens new perspectives for multidisciplinary applications at the frontier between materials science and nanomedicine. Here we present a novel hybrid nanosystem based on cytocompatible inorganic SiC/SiOx core/shell nanowires conjugated via click-chemistry procedures with an organic photosensitizer, a tetracarboxyphenyl porphyrin derivative. We show that this nanosystem is an efficient source of singlet oxygen for cell oxidative stress when irradiated with 6 MV X-Rays at low doses (0.4-2 Gy). The in-vitro clonogenic survival assay on lung adenocarcinoma cells shows that 12 days after irradiation at a dose of 2 Gy, the cell population is reduced by about 75% with respect to control cells. These results demonstrate that our approach is very efficient to enhance radiation therapy effects for cancer treatments.

Elemental compositions of crab and snail shells from the Kueishantao hydrothermal field in the southwestern Okinawa Trough

NASA Astrophysics Data System (ADS)

Zeng, Zhigang; Ma, Yao; Wang, Xiaoyuan; Chen, Chen-Tung Arthur; Yin, Xuebo; Zhang, Suping; Zhang, Junlong; Jiang, Wei

2018-04-01

To reveal differences in the behavior of benthic vent animals, and the sources and sinks of biogeochemical and fluid circulations, it is necessary to constrain the chemical characteristics of benthic animals from seafloor hydrothermal fields. We measured the abundances of 27 elements in shells of the crab Xenograpsus testudinatus and the snail Anachis sp., collected from the Kueishantao hydrothermal field (KHF) in the southwestern Okinawa Trough, with the aim of improving our understanding of the compositional variations between individual vent organisms, and the sources of the rare earth elements (REEs) in their shells. The Mn, Hg, and K concentrations in the male X. testudinatus shells are found to be higher than those in female crab shells, whereas the reverse is true for the accumulation of B, implying that the accumulation of K, Mn, Hg, and B in the crab shells is influenced by sex. This is inferred to be a result of the asynchronous molting of the male and female crab shells. Snail shells are found to have higher Ca, Al, Fe, Ni, and Co concentrations than crab shells. This may be attributed to different metal accumulation times. The majority of the light rare earth element (LREE) distribution patterns in the crab and snail shells are similar to those of Kueishantao vent fluids, with the crab and snail shells also exhibiting LREE enrichment, implying that the LREEs contained in crab and snail shells in the KHF are derived from vent fluids.

Rates of morphological evolution, asymmetry and morphological integration of shell shape in scallops.

PubMed

Sherratt, Emma; Serb, Jeanne M; Adams, Dean C

2017-12-08

Rates of morphological evolution vary across different taxonomic groups, and this has been proposed as one of the main drivers for the great diversity of organisms on Earth. Of the extrinsic factors pertaining to this variation, ecological hypotheses feature prominently in observed differences in phenotypic evolutionary rates across lineages. But complex organisms are inherently modular, comprising distinct body parts that can be differentially affected by external selective pressures. Thus, the evolution of trait covariation and integration in modular systems may also play a prominent role in shaping patterns of phenotypic diversity. Here we investigate the role ecological diversity plays in morphological integration, and the tempo of shell shape evolution and of directional asymmetry in bivalved scallops. Overall, the shape of both valves and the magnitude of asymmetry of the whole shell (difference in shape between valves) are traits that are evolving fast in ecomorphs under strong selective pressures (gliders, recessers and nestling), compared to low rates observed in other ecomorphs (byssal-attaching, free-living and cementing). Given that different parts of an organism can be under different selective pressures from the environment, we also examined the degree of evolutionary integration between the valves as it relates to ecological shifts. We find that evolutionary morphological integration is consistent and surprisingly high across species, indicating that while the left and right valves of a scallop shell are diversifying in accordance with ecomorphology, they are doing so in a concerted fashion. Our study on scallops adds another strong piece of evidence that ecological shifts play an important role in the tempo and mode of morphological evolution. Strong selective pressures from the environment, inferred from the repeated evolution of distinct ecomorphs, have influenced the rate of morphological evolution in valve shape and the magnitude of asymmetry between valves. Our observation that morphological integration of the valves making up the shell is consistently strong suggests tight developmental pathways are responsible for the concerted evolution of these structures while environmental pressures are driving whole shell shape. Finally, our study shows that directional asymmetry in shell shape among species is an important aspect of scallop macroevolution.

Enceladus's crust as a non-uniform thin shell: I tidal deformations

NASA Astrophysics Data System (ADS)

Beuthe, Mikael

2018-03-01

The geologic activity at Enceladus's south pole remains unexplained, though tidal deformations are probably the ultimate cause. Recent gravity and libration data indicate that Enceladus's icy crust floats on a global ocean, is rather thin, and has a strongly non-uniform thickness. Tidal effects are enhanced by crustal thinning at the south pole, so that realistic models of tidal tectonics and dissipation should take into account the lateral variations of shell structure. I construct here the theory of non-uniform viscoelastic thin shells, allowing for depth-dependent rheology and large lateral variations of shell thickness and rheology. Coupling to tides yields two 2D linear partial differential equations of the fourth order on the sphere which take into account self-gravity, density stratification below the shell, and core viscoelasticity. If the shell is laterally uniform, the solution agrees with analytical formulas for tidal Love numbers; errors on displacements and stresses are less than 5% and 15%, respectively, if the thickness is less than 10% of the radius. If the shell is non-uniform, the tidal thin shell equations are solved as a system of coupled linear equations in a spherical harmonic basis. Compared to finite element models, thin shell predictions are similar for the deformations due to Enceladus's pressurized ocean, but differ for the tides of Ganymede. If Enceladus's shell is conductive with isostatic thickness variations, surface stresses are approximately inversely proportional to the local shell thickness. The radial tide is only moderately enhanced at the south pole. The combination of crustal thinning and convection below the poles can amplify south polar stresses by a factor of 10, but it cannot explain the apparent time lag between the maximum plume brightness and the opening of tiger stripes. In a second paper, I will study the impact of a non-uniform crust on tidal dissipation.

Bioprinting Using Mechanically Robust Core-Shell Cell-Laden Hydrogel Strands.

PubMed

Mistry, Pritesh; Aied, Ahmed; Alexander, Morgan; Shakesheff, Kevin; Bennett, Andrew; Yang, Jing

2017-06-01

The strand material in extrusion-based bioprinting determines the microenvironments of the embedded cells and the initial mechanical properties of the constructs. One unmet challenge is the combination of optimal biological and mechanical properties in bioprinted constructs. Here, a novel bioprinting method that utilizes core-shell cell-laden strands with a mechanically robust shell and an extracellular matrix-like core has been developed. Cells encapsulated in the strands demonstrate high cell viability and tissue-like functions during cultivation. This process of bioprinting using core-shell strands with optimal biochemical and biomechanical properties represents a new strategy for fabricating functional human tissues and organs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vibrio cholerae Colonization of Soft-Shelled Turtles

PubMed Central

Wang, Jiazheng; Yan, Meiying; Gao, He; Lu, Xin

2017-01-01

ABSTRACT Vibrio cholerae is an important human pathogen and environmental microflora species that can both propagate in the human intestine and proliferate in zooplankton and aquatic organisms. Cholera is transmitted through food and water. In recent years, outbreaks caused by V. cholerae-contaminated soft-shelled turtles, contaminated mainly with toxigenic serogroup O139, have been frequently reported, posing a new foodborne disease public health problem. In this study, the colonization by toxigenic V. cholerae on the body surfaces and intestines of soft-shelled turtles was explored. Preferred colonization sites on the turtle body surfaces, mainly the carapace and calipash of the dorsal side, were observed for the O139 and O1 strains. Intestinal colonization was also found. The colonization factors of V. cholerae played different roles in the colonization of the soft-shelled turtle's body surface and intestine. Mannose-sensitive hemagglutinin (MSHA) of V. cholerae was necessary for body surface colonization, but no roles were found for toxin-coregulated pili (TCP) or N-acetylglucosamine-binding protein A (GBPA). Both TCP and GBPA play important roles for colonization in the intestine, whereas the deletion of MSHA revealed only a minor colonization-promoting role for this factor. Our study demonstrated that V. cholerae can colonize the surfaces and the intestines of soft-shelled turtles and indicated that the soft-shelled turtles played a role in the transmission of cholera. In addition, this study showed that the soft-shelled turtle has potential value as an animal model in studies of the colonization and environmental adaption mechanisms of V. cholerae in aquatic organisms. IMPORTANCE Cholera is transmitted through water and food. Soft-shelled turtles contaminated with Vibrio cholerae (commonly the serogroup O139 strains) have caused many foodborne infections and outbreaks in recent years, and they have become a foodborne disease problem. Except for epidemiological investigations, no experimental studies have demonstrated the colonization by V. cholerae on soft-shelled turtles. The present studies will benefit our understanding of the interaction between V. cholerae and the soft-shelled turtle. We demonstrated the colonization by V. cholerae on the soft-shelled turtle's body surface and in the intestine and revealed the different roles of major V. cholerae factors for colonization on the body surface and in the intestine. Our work provides experimental evidence for the role of soft-shelled turtles in cholera transmission. In addition, this study also shows the possibility for the soft-shelled turtle to serve as a new animal model for studying the interaction between V. cholerae and aquatic hosts. PMID:28600312

Vibrio cholerae Colonization of Soft-Shelled Turtles.

PubMed

Wang, Jiazheng; Yan, Meiying; Gao, He; Lu, Xin; Kan, Biao

2017-07-15

Vibrio cholerae is an important human pathogen and environmental microflora species that can both propagate in the human intestine and proliferate in zooplankton and aquatic organisms. Cholera is transmitted through food and water. In recent years, outbreaks caused by V. cholerae -contaminated soft-shelled turtles, contaminated mainly with toxigenic serogroup O139, have been frequently reported, posing a new foodborne disease public health problem. In this study, the colonization by toxigenic V. cholerae on the body surfaces and intestines of soft-shelled turtles was explored. Preferred colonization sites on the turtle body surfaces, mainly the carapace and calipash of the dorsal side, were observed for the O139 and O1 strains. Intestinal colonization was also found. The colonization factors of V. cholerae played different roles in the colonization of the soft-shelled turtle's body surface and intestine. Mannose-sensitive hemagglutinin (MSHA) of V. cholerae was necessary for body surface colonization, but no roles were found for toxin-coregulated pili (TCP) or N -acetylglucosamine-binding protein A (GBPA). Both TCP and GBPA play important roles for colonization in the intestine, whereas the deletion of MSHA revealed only a minor colonization-promoting role for this factor. Our study demonstrated that V. cholerae can colonize the surfaces and the intestines of soft-shelled turtles and indicated that the soft-shelled turtles played a role in the transmission of cholera. In addition, this study showed that the soft-shelled turtle has potential value as an animal model in studies of the colonization and environmental adaption mechanisms of V. cholerae in aquatic organisms. IMPORTANCE Cholera is transmitted through water and food. Soft-shelled turtles contaminated with Vibrio cholerae (commonly the serogroup O139 strains) have caused many foodborne infections and outbreaks in recent years, and they have become a foodborne disease problem. Except for epidemiological investigations, no experimental studies have demonstrated the colonization by V. cholerae on soft-shelled turtles. The present studies will benefit our understanding of the interaction between V. cholerae and the soft-shelled turtle. We demonstrated the colonization by V. cholerae on the soft-shelled turtle's body surface and in the intestine and revealed the different roles of major V. cholerae factors for colonization on the body surface and in the intestine. Our work provides experimental evidence for the role of soft-shelled turtles in cholera transmission. In addition, this study also shows the possibility for the soft-shelled turtle to serve as a new animal model for studying the interaction between V. cholerae and aquatic hosts. Copyright © 2017 American Society for Microbiology.

Nonbibliographic Databases in a Corporate Health, Safety, and Environment Organization.

ERIC Educational Resources Information Center

Cubillas, Mary M.

1981-01-01

Summarizes the characteristics of TOXIN, CHEMFILE, and the Product Profile Information System (PPIS), nonbibliographic databases used by Shell Oil Company's Health, Safety, and Environment Organization. (FM)

Nevirapine Loaded Core Shell Gold Nanoparticles by Double Emulsion Solvent Evaporation: In vitro and In vivo Evaluation.

PubMed

Dalvi, Bhagyashree R; Siddiqui, Ejaz A; Syed, Asad S; Velhal, Shilpa M; Ahmad, Absar; Bandivdekar, Atmaram B; Devarajan, Padma V

2016-01-01

HIV/AIDS is a macrophage resident infection localized in the reticuloendothelial system and remote locations of brain and bone marrow. We present core shell nanoparticles of gold(AuNPs) and nevirapine(NVP) for targeted delivery to the multiple HIV reservoirs. The aim of the study was to design core shell NVP loaded AuNPs with high drug loading and to evaluate biodistribution of the nanoparticles in possible HIV reservoirs in vivo. A specific objective was to assess the possible synergy of AuNPs with NVP on anti-HIV activity in vitro. Core shell nanoparticles were prepared by double emulsion solvent evaporation method and characterized. Glyceryl monostearate-nevirapine-gold nanoparticles(GMS-NVP-AuNPs) revealed high entrapment efficiency (>70%), high loading (~40%), particle size <250 nm and zeta potential -35.9± 1.41mv and exhibited sustained release with good stability. Surface plasmon resonance indicated shell formation while SEM coupled EDAX confirmed the presence of Au. TEM confirmed formation of spherical core shell nanoparticles. GMS-NVP-AuNPs revealed low hemolysis (<10 %) and serum stability upto 6 h. GMS-NVP-AuNPs exhibited rapid, high and sustained accumulation in the possible HIV reservoir organs, including the major organs of liver, spleen, lymph nodes, thymus and also remote locations of brain, ovary and bone marrow. High cell viability and enhanced uptake in PBMC's and TZM-bl cells were observed. While uptake in PBMC's proposed monocytes/macrophages enabled brain delivery. GMS-NVP-AuNPs demonstrated synergistic anti-HIV activity. The superior anti-HIV activity in vitro coupled with extensive localization of the nanoparticles in multiple HIV reservoirs suggests great promise of the core shell GMS-NVP-AuNPs for improved therapy of HIV.

Enhance the photoluminescence and radioluminescence of La2Zr2O7:Eu3+ core nanoparticles by coating with a thin Y2O3 shell

NASA Astrophysics Data System (ADS)

Pokhrel, Madhab; Burger, Arnold; Groza, Michael; Mao, Yuanbing

2017-06-01

We report the generation of La2Zr2O7:5%Eu3+@Y2O3 (LZO5E@YO) core@shell crystalline inorganic-inorganic heterogeneous nanoparticles (NPs). The Y2O3 (YO) shell coating process based on a chemical sol-gel method led to the growth of a thin YO shell on the ordered pyrochlore La2Zr2O7:5%Eu3+ (LZO5E) core NPs. Photoluminescence (PL) analyses demonstrated a blue shift of 15 nm on charge transfer (CT) excitation band of the core@shell NPs from that of the core NPs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) along x-ray diffraction (XRD), Fourier-transform Infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) studies confirmed the formation of the thin YO layer over the LZO5E core NPs. The PL intensity of the LZO5E@YO core@shell NPs was enhanced by three fold compared to that of the LZO5E core NPs, and higher quantum yield (QY) was observed for the former compared to the original NPs by more than 70%. Higher radioluminescence (RL) emission was also observed for the core@shell NPs compared to the core NPs. Our ability of obtaining near-perfect core@shell heterostructure with enhanced luminescence performance opens the door for the development of efficient La2Zr2O7:5%Eu3+@Y2O3 NPs for both optical and x-ray scintillation applications.

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.

Analysis of Benthic Foraminiferal Size Change During the Eocene-Oligocene Transition

NASA Astrophysics Data System (ADS)

Zachary, W.; Keating-Bitonti, C.

2017-12-01

The Eocene-Oligocene transition is a significant global cooling event with the first growth of continental ice on Antarctica. In the geologic record, the size of fossils can be used to indirectly observe how organisms respond to climate change. For example, organisms tend to be larger in cooler environments as a physiological response to temperature. This major global cooling event should influence organism physiology, resulting in significant size trends observed in the fossil record. Benthic foraminifera are protists and those that grow a carbonate shell are both well-preserved and abundant in marine sediments. Here, we used the foraminiferal fossil record to study the relationship between their size and global cooling. We hypothesize that cooler temperatures across the Eocene-Oligocene boundary promoted shell size increase. To test this hypothesis, we studied benthic foraminifera from 10 deep-sea cores drilled at Ocean Drilling Program Site 744, located in the southern Indian Ocean. We washed sediment samples over a 63-micron sieve and picked foraminifera from a 125-micron sieve. We studied the benthic foraminiferal genus Cibicidoides and its size change across this cooling event. Picked specimens were imaged and we measured the diameter of their shells using "imageJ". Overall, we find that Cibicidoides shows a general trend of increasing size during this transition. In particular, both the median and maximum sizes of Cibicidoides increase from the Eocene into the Oligocene. We also analyzed C. pachyderma and C. mundulus for size trends. Although both species increase in median size across the boundary, only C. pachyderma shows a consistent trend of increasing maximum, median, and minimum shell diameter. After the Eocene-Oligocene boundary, we observe that shell diameter decreases following peak cooling and that foraminiferal sizes remain stable into the early Oligocene. Therefore, the Eocene-Oligocene cooling event appears to have strong influence on shell size.

Fabrication of core-shell Fe{sub 3}O{sub 4}@MIL-100(Fe) magnetic microspheres for the removal of Cr(VI) in aqueous solution

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

Yang, Qingxiang, E-mail: qxyangzz@163.com; Zhao, Qianqian; Ren, ShuangShuang

Facile regeneration of an adsorbent is very important for commercial feasibility. One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) with diameter about of 350 nm were successfully synthesized. The growth of MIL-100(Fe) shell on the surface of Fe{sub 3}O{sub 4} was utilized precursor as crystal seed via in-situ step hydrothermal reaction. It is a simple way to obtain well organized core-shell MOF composites, compared to the step-by-step method. MMCs were firstly used to uptake of Cr(VI) anions in aqueous solution. Adsorption experiments were carried out in batch sorption mode investigatingmore » with the factors of contact time (0–1000 min), pH (from 2 to 12), dose of adsorbent (4–25 mg), and initial Cr(VI) concentration (range from 10 to 100 ppm). - Graphical abstract: One typical highly porous metal-organic framework (MOF) materials based on MIL-100(Fe) and magnetic iron oxide particles (denoted as MMCs) were successfully synthesized. Utilizing Fe{sub 3}O{sub 4} precursor as crystal seed to grow MIL-100(Fe) shell by in-situ step hydrothermal reaction. It is a simple way to obtain core-shell MOF composites. MMCs could effectively uptake of Cr(VI) anions in aqueous solution. - Highlights: • Fe{sub 3}O{sub 4}@MIL-100(Fe) composites with core-shell structure were successfully prepared through a simple method. • The influence factors on Cr(VI) adsorption by Fe{sub 3}O{sub 4}@MIL-100(Fe) were investigated. • Cr(VI) can efficiently adsorbed by Fe{sub 3}O{sub 4}@MIL-100(Fe) composites from aqueous solution.« less

Molecular basis for competitive solvation of the Burkholderia cepacia lipase by sorbitol and urea.

PubMed

Oliveira, Ivan P; Martínez, Leandro

2016-08-21

Increasing the stability of proteins is important for their application in industrial processes. In the intracellular environment many small molecules, called osmolytes, contribute to protein stabilization under physical or chemical stress. Understanding the nature of the interactions of these osmolytes with proteins can help the design of solvents and mutations to increase protein stability in extracellular media. One of the most common stabilizing osmolyes is sorbitol and one of the most common chemical denaturants is urea. In this work, we use molecular dynamics simulations to obtain a detailed picture of the solvation of the Burkholderia cepacia lipase (BCL) in the presence of the protecting osmolyte sorbitol and of the urea denaturant. We show that both sorbitol and urea compete with water for interactions with the protein surface. Overall, sorbitol promotes the organization of water in the first solvation shell and displaces water from the second solvation shell, while urea causes opposite effects. These effects are, however, highly heterogeneous among residue types. For instance, the depletion of water from the first protein solvation shell by urea can be traced down essentially to the side chain of negatively charged residues. The organization of water in the first solvation shell promoted by sorbitol occurs at polar (but not charged) residues, where the urea effect is minor. By contrast, sorbitol depletes water from the second solvation shell of polar residues, while urea promotes water organization at the same distances. The interactions of urea with negatively charged residues are insensitive to the presence of sorbitol. This osmolyte removes water and urea particularly from the second solvation shell of polar and non-polar residues. In summary, we provide a comprehensive description of the diversity of protein-solvent interactions, which can guide further investigations on the stability of proteins in non-conventional media, and assist solvent and protein design.

Variation in Orthologous Shell-Forming Proteins Contribute to Molluscan Shell Diversity

PubMed Central

Jackson, Daniel J.; Reim, Laurin; Randow, Clemens; Cerveau, Nicolas; Degnan, Bernard M.; Fleck, Claudia

2017-01-01

Abstract Despite the evolutionary success and ancient heritage of the molluscan shell, little is known about the molecular details of its formation, evolutionary origins, or the interactions between the material properties of the shell and its organic constituents. In contrast to this dearth of information, a growing collection of molluscan shell-forming proteomes and transcriptomes suggest they are comprised of both deeply conserved, and lineage specific elements. Analyses of these sequence data sets have suggested that mechanisms such as exon shuffling, gene co-option, and gene family expansion facilitated the rapid evolution of shell-forming proteomes and supported the diversification of this phylum specific structure. In order to further investigate and test these ideas we have examined the molecular features and spatial expression patterns of two shell-forming genes (Lustrin and ML1A2) and coupled these observations with materials properties measurements of shells from a group of closely related gastropods (abalone). We find that the prominent “GS” domain of Lustrin, a domain believed to confer elastomeric properties to the shell, varies significantly in length between the species we investigated. Furthermore, the spatial expression patterns of Lustrin and ML1A2 also vary significantly between species, suggesting that both protein architecture, and the regulation of spatial gene expression patterns, are important drivers of molluscan shell evolution. Variation in these molecular features might relate to certain materials properties of the shells of these species. These insights reveal an important and underappreciated source of variation within shell-forming proteomes that must contribute to the diversity of molluscan shell phenotypes. PMID:28961798

A general and high-yield galvanic displacement approach to Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells and enhanced electrocatalytic performances.

PubMed

Kuai, Long; Geng, Baoyou; Wang, Shaozhen; Sang, Yan

2012-07-23

In this work, we utilize the galvanic displacement synthesis and make it a general and efficient method for the preparation of Au-M (M = Au, Pd, and Pt) core-shell nanostructures with porous shells, which consist of multilayer nanoparticles. The method is generally applicable to the preparation of Au-Au, Au-Pd, and Au-Pt core-shell nanostructures with typical porous shells. Moreover, the Au-Au isomeric core-shell nanostructure is reported for the first time. The lower oxidation states of Au(I), Pd(II), and Pt(II) are supposed to contribute to the formation of porous core-shell nanostructures instead of yolk-shell nanostructures. The electrocatalytic ethanol oxidation and oxygen reduction reaction (ORR) performance of porous Au-Pd core-shell nanostructures are assessed as a typical example for the investigation of the advantages of the obtained core-shell nanostructures. As expected, the Au-Pd core-shell nanostructure indeed exhibits a significantly reduced overpotential (the peak potential is shifted in the positive direction by 44 mV and 32 mV), a much improved CO tolerance (I(f)/I(b) is 3.6 and 1.63 times higher), and an enhanced catalytic stability in comparison with Pd nanoparticles and Pt/C catalysts. Thus, porous Au-M (M = Au, Pd, and Pt) core-shell nanostructures may provide many opportunities in the fields of organic catalysis, direct alcohol fuel cells, surface-enhanced Raman scattering, and so forth. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling Optical and Radiative Properties of Clouds Constrained with CARDEX Observations

NASA Astrophysics Data System (ADS)

Mishra, S. K.; Praveen, P. S.; Ramanathan, V.

2013-12-01

Carbonaceous aerosols (CA) have important effects on climate by directly absorbing solar radiation and indirectly changing cloud properties. These particles tend to be a complex mixture of graphitic carbon and organic compounds. The graphitic component, called as elemental carbon (EC), is characterized by significant absorption of solar radiation. Recent studies showed that organic carbon (OC) aerosols absorb strongly near UV region, and this faction is known as Brown Carbon (BrC). The indirect effect of CA can occur in two ways, first by changing the thermal structure of the atmosphere which further affects dynamical processes governing cloud life cycle; secondly, by acting as cloud condensation nuclei (CCN) that can change cloud radiative properties. In this work, cloud optical properties have been numerically estimated by accounting for CAEDEX (Cloud Aerosol Radiative Forcing Dynamics Experiment) observed cloud parameters and the physico-chemical and optical properties of aerosols. The aerosol inclusions in the cloud drop have been considered as core shell structure with core as EC and shell comprising of ammonium sulfate, ammonium nitrate, sea salt and organic carbon (organic acids, OA and brown carbon, BrC). The EC/OC ratio of the inclusion particles have been constrained based on observations. Moderate and heavy pollution events have been decided based on the aerosol number and BC concentration. Cloud drop's co-albedo at 550nm was found nearly identical for pure EC sphere inclusions and core-shell inclusions with all non-absorbing organics in the shell. However, co-albedo was found to increase for the drop having all BrC in the shell. The co-albedo of a cloud drop was found to be the maximum for all aerosol present as interstitial compare to 50% and 0% inclusions existing as interstitial aerosols. The co-albedo was found to be ~ 9.87e-4 for the drop with 100% inclusions existing as interstitial aerosols externally mixed with micron size mineral dust with 2% hematite content. The cloud spectral optical properties and the radiative properties for the aforesaid cases during CARDEX observations will be discussed in detail.

Fate of the open-shell singlet ground state in the experimentally accessible acenes: A quantum Monte Carlo study

NASA Astrophysics Data System (ADS)

Dupuy, Nicolas; Casula, Michele

2018-04-01

By means of the Jastrow correlated antisymmetrized geminal power (JAGP) wave function and quantum Monte Carlo (QMC) methods, we study the ground state properties of the oligoacene series, up to the nonacene. The JAGP is the accurate variational realization of the resonating-valence-bond (RVB) ansatz proposed by Pauling and Wheland to describe aromatic compounds. We show that the long-ranged RVB correlations built in the acenes' ground state are detrimental for the occurrence of open-shell diradical or polyradical instabilities, previously found by lower-level theories. We substantiate our outcome by a direct comparison with another wave function, tailored to be an open-shell singlet (OSS) for long-enough acenes. By comparing on the same footing the RVB and OSS wave functions, both optimized at a variational QMC level and further projected by the lattice regularized diffusion Monte Carlo method, we prove that the RVB wave function has always a lower variational energy and better nodes than the OSS, for all molecular species considered in this work. The entangled multi-reference RVB state acts against the electron edge localization implied by the OSS wave function and weakens the diradical tendency for higher oligoacenes. These properties are reflected by several descriptors, including wave function parameters, bond length alternation, aromatic indices, and spin-spin correlation functions. In this context, we propose a new aromatic index estimator suitable for geminal wave functions. For the largest acenes taken into account, the long-range decay of the charge-charge correlation functions is compatible with a quasi-metallic behavior.

Thickness Constraints on the Icy Shells of the Galilean Satellites from a Comparison of Crater Shapes

NASA Technical Reports Server (NTRS)

Schenk, Paul M.

2002-01-01

A thin outer ice shell on Jupiter's large moon Europa would imply easy exchange between the surface and any organic or biotic material in its putative subsurface ocean. The thickness of the outer ice shell is poorly constrained, however, with model-dependent estimates ranging from a few kilometers of depths of impact craters on Europa, Ganymede and Callisto that reveal two anomalous transitions in crater shape with diameter. The first transition is probably related to temperature-dependent ductility of the crust at shallow depths (7-8 km on Europa). The second transition is attributed to the influence of subsurface oceans on all three satellites, which constrains Europa's icy shell to be at least 19 km thick. The icy lithospheres of Ganymede and Callisto are equally ice-rich, but Europa's icy shell has a thermal structure about 0.25-0.5 times the thickness of Ganymede's or Callisto's shells, depending on epoch. The appearances of the craters on Europa are inconsistent with thin-ice-shell models and indicate that exchange of oceanic and surface material could be difficult.

Influence of heat treatment on hole transfer dynamics in core-shell quantum dot/organic hole conductor hybrid films

NASA Astrophysics Data System (ADS)

Sun, Mingye; Zheng, Youjin; Zhang, Lei; Zhao, Liping; Zhang, Bing

2017-08-01

The influence of heat treatment on hole transfer (HT) processes from the CdSe/ZnS and CdSe/CdS/ZnS quantum dots (QDs) to 4,4‧,4″-Tris(carbazol-9-yl)-triphenylamine (TCTA) in QD/TCTA hybrid films has been researched with time-resolved photoluminescence (PL) spectroscopy. The PL dynamic results demonstrated a heat-treatment-temperature-dependent HT process from the core-shell CdSe QDs to TCTA. The HT rates and efficiencies can be effectively increased due to reduced distance between core-shell CdSe QDs and TCTA after heat treatment. The CdS shell exhibited a more obvious effect on HT from the core-shell CdSe QDs to TCTA than on electron transfer to TiO2, due to higher barrier for holes to tunnel through CdS shell and larger effective mass of holes in CdS than electrons. These results indicate that heat treatment would be an effective means to further optimize solid-state QD sensitized solar cells and rational design of CdS shell is significant.

History of bioavailable lead and iron in the Greater North Sea and Iceland during the last millennium - a bivalve sclerochronological reconstruction.

PubMed

Holland, Hilmar A; Schöne, Bernd R; Marali, Soraya; Jochum, Klaus P

2014-10-15

We present the first annually resolved record of biologically available Pb and Fe in the Greater North Sea and Iceland during 1040-2004 AD based on shells of the long-lived marine bivalve Arctica islandica. The iron content in pre-industrial shells from the North Sea largely remained below the detection limit. Only since 1830, shell Fe levels rose gradually reflecting the combined effect of increased terrestrial runoff of iron-bearing sediments and eutrophication. Although the lead gasoline peak of the 20th century was well recorded by the shells, bivalves that lived during the medieval heyday of metallurgy showed four-fold higher shell Pb levels than modern specimens. Presumably, pre-industrial bivalves were offered larger proportions of resuspended (Pb-enriched) organics, whereas modern specimens receive fresh increased amounts of (Pb-depleted) phytoplankton. As expected, metal loads in the shells from Iceland were much lower. Our study confirms that bivalve shells provide a powerful tool for retrospective environmental biomonitoring. Copyright © 2014 Elsevier Ltd. All rights reserved.

Shell extracts from the marine bivalve Pecten maximus regulate the synthesis of extracellular matrix in primary cultured human skin fibroblasts.

PubMed

Latire, Thomas; Legendre, Florence; Bigot, Nicolas; Carduner, Ludovic; Kellouche, Sabrina; Bouyoucef, Mouloud; Carreiras, Franck; Marin, Frédéric; Lebel, Jean-Marc; Galéra, Philippe; Serpentini, Antoine

2014-01-01

Mollusc shells are composed of more than 95% calcium carbonate and less than 5% of an organic matrix consisting mostly of proteins, glycoproteins and polysaccharides. Previous studies have elucidated the biological activities of the shell matrices from bivalve molluscs on skin, especially on the expression of the extracellular matrix components of fibroblasts. In this work, we have investigated the potential biological activities of shell matrix components extracted from the shell of the scallop Pecten maximus on human fibroblasts in primary culture. Firstly, we demonstrated that shell matrix components had different effects on general cellular activities. Secondly, we have shown that the shell matrix components stimulate the synthesis of type I and III collagens, as well as that of sulphated GAGs. The increased expression of type I collagen is likely mediated by the recruitment of transactivating factors (Sp1, Sp3 and human c-Krox) in the -112/-61 bp COL1A1 promoter region. Finally, contrarily to what was obtained in previous works, we demonstrated that the scallop shell extracts have only a small effect on cell migration during in vitro wound tests and have no effect on cell proliferation. Thus, our research emphasizes the potential use of shell matrix of Pecten maximus for dermo-cosmetic applications.

The functional divide for primary reinforcement of D-amphetamine lies between the medial and lateral ventral striatum: is the division of the accumbens core, shell, and olfactory tubercle valid?

PubMed

Ikemoto, Satoshi; Qin, Mei; Liu, Zhong-Hua

2005-05-18

When projection analyses placed the nucleus accumbens and olfactory tubercle in the striatal system, functional links between these sites began to emerge. The accumbens has been implicated in the rewarding effects of psychomotor stimulants, whereas recent work suggests that the medial accumbens shell and medial olfactory tubercle mediate the rewarding effects of cocaine. Interestingly, anatomical evidence suggests that medial portions of the shell and tubercle receive afferents from common zones in a number of regions. Here, we report results suggesting that the current division of the ventral striatum into the accumbens core and shell and the olfactory tubercle does not reflect the functional organization for amphetamine reward. Rats quickly learned to self-administer D-amphetamine into the medial shell or medial tubercle, whereas they failed to learn to do so into the accumbens core, ventral shell, or lateral tubercle. Our results suggest that primary reinforcement of amphetamine is mediated via the medial portion of the ventral striatum. Thus, the medial shell and medial tubercle are more functionally related than the medial and ventral shell or the medial and lateral tubercle. The current core-shell-tubercle scheme should be reconsidered in light of recent anatomical data and these functional findings.

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

A Bottle-around-a-Ship Method To Generate Hollow Thin-Shelled Particles Containing Encapsulated Iron Species with Application to the Environmental Decontamination of Chlorinated Compounds.

PubMed

Su, Yang; Wang, Yingqing; Owoseni, Olasehinde; Zhang, Yueheng; Gamliel, David Pierce; Valla, Julia A; McPherson, Gary L; John, Vijay T

2018-04-25

Thin-shelled hollow silica particles are synthesized using an aerosol-based process where the concentration of a silica precursor tetraethyl orthosilicate (TEOS) determines the shell thickness. The synthesis involves a novel concept of the salt bridging of an iron salt, FeCl 3 , to a cationic surfactant, cetyltrimethylammonium bromide (CTAB), which modulates the templating effect of the surfactant on silica porosity. The salt bridging leads to a sequestration of the surfactant in the interior of the droplet with the formation of a dense silica shell around the organic material. Subsequent calcination consistently results in hollow particles with encapsulated iron oxides. Control of the TEOS levels leads to the generation of ultrathin-shelled (∼10 nm) particles which become susceptible to rupture upon exposure to ultrasound. The dense silica shell that is formed is impervious to entry of chemical species. Mesoporosity is restored to the shell through desilication and reassembly, again using CTAB as a template. The mesoporous-shelled hollow particles show good reactivity toward the reductive dichlorination of trichloroethylene (TCE), indicating access of TCE to the particle interior. The ordered mesoporous thin-shelled particles containing active iron species are viable systems for chemical reaction and catalysis.

One-Pot Synthesis of Tunable Crystalline Ni3 S4 @Amorphous MoS2 Core/Shell Nanospheres for High-Performance Supercapacitors.

PubMed

Zhang, Yu; Sun, Wenping; Rui, Xianhong; Li, Bing; Tan, Hui Teng; Guo, Guilue; Madhavi, Srinivasan; Zong, Yun; Yan, Qingyu

2015-08-12

Transition metal sulfides gain much attention as electrode materials for supercapacitors due to their rich redox chemistry and high electrical conductivity. Designing hierarchical nanostructures is an efficient approach to fully utilize merits of each component. In this work, amorphous MoS(2) is firstly demonstrated to show specific capacitance 1.6 times as that of the crystalline counterpart. Then, crystalline core@amorphous shell (Ni(3)S(4)@MoS(2)) is prepared by a facile one-pot process. The diameter of the core and the thickness of the shell can be independently tuned. Taking advantages of flexible protection of amorphous shell and high capacitance of the conductive core, Ni(3)S(4) @amorphous MoS(2) nanospheres are tested as supercapacitor electrodes, which exhibit high specific capacitance of 1440.9 F g(-1) at 2 A g(-1) and a good capacitance retention of 90.7% after 3000 cycles at 10 A g(-1). This design of crystalline core@amorphous shell architecture may open up new strategies for synthesizing promising electrode materials for supercapacitors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organ size control via hydraulically gated oscillations.

PubMed

Ruiz-Herrero, Teresa; Alessandri, Kévin; Gurchenkov, Basile V; Nassoy, Pierre; Mahadevan, L

2017-12-01

Hollow vesicular tissues of various sizes and shapes arise in biological organs such as ears, guts, hearts, brains and even entire organisms. Regulating their size and shape is crucial for their function. Although chemical signaling has been thought to play a role in the regulation of cellular processes that feed into larger scales, it is increasingly recognized that mechanical forces are involved in the modulation of size and shape at larger length scales. Motivated by a variety of examples of tissue cyst formation and size control that show simultaneous growth and size oscillations, we create a minimal theoretical framework for the growth and dynamics of a soft, fluid-permeable, spherical shell. We show that these shells can relieve internal pressure by bursting intermittently, shrinking and re-growing, providing a simple mechanism by which hydraulically gated oscillations can regulate size. To test our theory, we develop an in vitro experimental set-up to monitor the growth and oscillations of a hollow tissue spheroid growing freely or when confined. A simple generalization of our theory to account for irreversible deformations allows us to explain the time scales and the amplitudes of oscillations in terms of the geometry and mechanical properties of the tissue shells. Taken together, our theory and experimental observations show how soft hydraulics can regulate the size of growing tissue shells. © 2017. Published by The Company of Biologists Ltd.

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.

Direct characterization of the native structure and mechanics of cyanobacterial carboxysomes.

PubMed

Faulkner, Matthew; Rodriguez-Ramos, Jorge; Dykes, Gregory F; Owen, Siân V; Casella, Selene; Simpson, Deborah M; Beynon, Robert J; Liu, Lu-Ning

2017-08-03

Carboxysomes are proteinaceous organelles that play essential roles in enhancing carbon fixation in cyanobacteria and some proteobacteria. These self-assembling organelles encapsulate Ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco) and carbonic anhydrase using a protein shell structurally resembling an icosahedral viral capsid. The protein shell serves as a physical barrier to protect enzymes from the cytosol and a selectively permeable membrane to mediate transport of enzyme substrates and products. The structural and mechanical nature of native carboxysomes remain unclear. Here, we isolate functional β-carboxysomes from the cyanobacterium Synechococcus elongatus PCC7942 and perform the first characterization of the macromolecular architecture and inherent physical mechanics of single β-carboxysomes using electron microscopy, atomic force microscopy (AFM) and proteomics. Our results illustrate that the intact β-carboxysome comprises three structural domains, a single-layered icosahedral shell, an inner layer and paracrystalline arrays of interior Rubisco. We also observe the protein organization of the shell and partial β-carboxysomes that likely serve as the β-carboxysome assembly intermediates. Furthermore, the topography and intrinsic mechanics of functional β-carboxysomes are determined in native conditions using AFM and AFM-based nanoindentation, revealing the flexible organization and soft mechanical properties of β-carboxysomes compared to rigid viruses. Our study provides new insights into the natural characteristics of β-carboxysome organization and nanomechanics, which can be extended to diverse bacterial microcompartments and are important considerations for the design and engineering of functional carboxysomes in other organisms to supercharge photosynthesis. It offers an approach for inspecting the structural and mechanical features of synthetic metabolic organelles and protein scaffolds in bioengineering.

One dimensional CdS nanowire@TiO2 nanoparticles core-shell as high performance photocatalyst for fast degradation of dye pollutants under visible and sunlight irradiation.

PubMed

Arabzadeh, Abbas; Salimi, Abdollah

2016-10-01

In this study, one-dimensional CdS nanowires@TiO2 nanoparticles core-shell structures (1D CdS NWs@TiO2 NPs) were synthesized by a facile wet chemical-solvothermal method. The different aspects of the properties of CdS NWs@TiO2 NPs were surveyed by using a comprehensive range of characterization techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV-vis spectroscopy, scanning electron microscopy (SEM), fluorescence spectroscopy, energy dispersive X-ray spectroscopy (EDX), Cyclic Voltammetry (CV) and amperometry. The as-prepared nanostructure was applied as an effective photocatalyst for degradation of methyl orange (MO), methylene blue (MB) and rhodamine B (Rh B) under visible and sunlight irradiation. The results indicated significantly enhanced photocatalytic activity of CdS NWs@TiO2 NPs for degradation of MO, MB and Rh B compared to CdS NWs. The enhanced photocatalytic activity could be attributed to the enhanced sunlight absorbance and the efficient charge separation of the formed heterostructure between CdS NWs and TiO2. The results showed that MO, Rh B and MB were almost completely degraded after 2, 2 and 3min of exposure to sunlight, respectively; while under visible light irradiation (3W blue LED lamp) the dyes were decomposed with less half degradation rate. The catalytic activity was retained even after three degradation cycles of organic dyes, demonstrating that the proposed nanocomposite can be effectively used as efficient photocatalyst for removal of environmental pollutions caused by organic dyes under sunlight irradiation and it could be an important addition to the field of wastewater treatment. We hope the present study may open a new window of such 1-D semiconductor nanocomposites to be used as visible light photocatalysts in the promising field of organic dyes degradation. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

A comparison of the solvation structure and dynamics of the lithium ion in linear organic carbonates with different alkyl chain lengths.

PubMed

Fulfer, K D; Kuroda, D G

2017-09-20

The structure and dynamics of electrolytes composed of lithium hexafluorophosphate (LiPF 6 ) in dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate were investigated using a combination of linear and two-dimensional infrared spectroscopies. The solutions studied here have a LiPF 6 concentration of X(LiPF 6 ) = 0.09, which is typically found in commercial lithium ion batteries. This study focuses on comparing the differences in the solvation shell structure and dynamics produced by linear organic carbonates of different alkyl chain lengths. The IR experiments show that either linear carbonate forms a tetrahedral solvation shell (coordination number of 4) around the lithium ion irrespective of whether the solvation shell has anions in close proximity to the carbonates. Moreover, analysis of the absorption cross sections via FTIR and DFT computations reveals a distortion in the angle formed by Li + -O[double bond, length as m-dash]C which decreases from the expected 180° when the alkyl chains of the carbonate are lengthened. In addition, our findings also reveal that, likely due to its asymmetric structure, ethyl methyl carbonate has a significantly more distorted tetrahedral lithium ion solvation shell than either of the other two investigated carbonates. IR photon echo studies further demonstrate that the motions of the solvation shell have a time scale of a few picoseconds for all three linear carbonates. Interestingly, a slowdown of the in place-motions of the first solvation shell is observed when the carbonate has a longer alkyl chain length irrespective of the symmetry. In addition, vibrational energy transfer with a time scale of tens of picoseconds is observed between strongly coupled modes arising from the solvation shell structure of the Li + which corroborates the modeling of these solvation shells in terms of highly coupled vibrational states. Results of this study provide new insights into the molecular structure and dynamics of the lithium ion electrolyte components as a function of solvent structure.

Ecophysiology of the hydrothermal vent snail Ifremeria nautilei and barnacle Eochionelasmus ohtai manusensis, Manus Basin, Papua New Guinea: Insights from shell mineralogy and stable isotope geochemistry

NASA Astrophysics Data System (ADS)

Bojar, Ana-Voica; Lécuyer, Christophe; Bojar, Hans-Peter; Fourel, François; Vasile, Ştefan

2018-03-01

Deep-sea vent communities live on a limited area characterized by sharp physico-chemical (temperature, salinity, pH) gradients. Around the vent, the fauna is distributed accordingly, showing characteristic niche partitioning for different groups of animals. In this study we investigate shell microstructure, minor elements and stable isotope compositions of two groups of organisms such as a snail, Ifremeria nautilei, and a crustacean, Eochionelasmus ohtai manusensis. Both organisms occupy distinct niches within the same hydrothermal vent field of the Manus Basin, Western Pacific. Powder XRD and electron microbeam analysis of a polished cross-section indicate that the shells are composed of microcrystalline calcite, with distinct Na, Mg, Sr, and S element contents. For both specimens 20-30 μm large weddellite crystals were found. The δ18O profiles were obtained perpendicular to the growth increments of I. nautilei and E. o. manusensis calcitic shells. Those profiles reveal isotopic variations of 0.5 and 0.6‰, respectively for both intra- and inter-shell measurements. For E. o. manusensis, the Mg content suggests continuous shell growth during the year, both δ18O and Mg data supporting cyclical variation of temperature at vent site. The calculated temperatures at sites with I. nautilei and E. o. manusensis range from 17° to 21.5°C and from 2.1° to 7.2°C, respectively, showing a similar variability of 5-6 °C. The δ13C values of the Ifremeria calcitic shell range from 3‰ to 4.6‰ (V-PDB), the isotopic composition being 13C-enriched relative to the surrounding inorganic pool. The δ13C values of the chitine layer covering the shell range from - 33 to - 31.1‰. The δ13C values of Eochionelasmus vary between 0‰ and 1‰, reflecting the surrounding inorganic DIC pool.

The Structure of Isolated Synechococcus Strain WH8102 Carboxysomes as Revealed by Electron Cryotomography

PubMed Central

Iancu, Cristina V.; Ding, H. Jane; Morris, Dylan M.; Dias, D. Prabha; Gonzales, Arlene D.; Martino, Anthony; Jensen, Grant J.

2007-01-01

Carboxysomes are organelle-like polyhedral bodies found in cyanobacteria and many chemoautotrophic bacteria that are thought to facilitate carbon fixation. Carboxysomes are bounded by a proteinaceous outer shell and filled with ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO), the first enzyme in the CO2 fixation pathway, but exactly how they enhance carbon fixation is unclear. Here we report the three-dimensional structure of purified carboxysomes from Synechococcus species strain WH8102 as revealed by electron cryotomography. We found that while the sizes of individual carboxysomes in this organism varied from 114 to 137 nm, surprisingly, all were approximately icosahedral. There were on average ∼250 RuBisCOs per carboxysome, organized into 3-4 concentric layers. Some models of carboxysome function depend on specific contacts between individual RuBisCOs and the shell, but no evidence of such contacts was found: no systematic patterns of connecting densities or RuBisCO positions against the shell's presumed hexagonal lattice could be discerned, and simulations showed that packing forces alone could account for the layered organization of RuBisCOs. PMID:17669419

Aragonite-Associated Mollusk Shell Protein Aggregates To Form Mesoscale “Smart” Hydrogels

DOE PAGES

Perovic, Iva; Davidyants, Anastasia; Evans, John Spencer

2016-11-30

In the mollusk shell there exists a framework silk fibroin-polysaccharide hydrogel coating around nacre aragonite tablets, and this coating facilitates the synthesis and organization of mineral nanoparticles into mesocrystals. In this report, we identify that a protein component of this coating, n16.3, is a hydrogelator. Due to the presence of intrinsic disorder, aggregation-prone regions, and nearly equal balance of anionic and cationic side chains, this protein assembles to form porous mesoscale hydrogel particles in solution and on mica surfaces. These hydrogel particles change their dimensionality, organization, and internal structure in response to pH and ions, particularly Ca(II), which indicates thatmore » these behave as ion-responsive or “smart” hydrogels. Thus, in addition to silk fibroins, the gel phase of the mollusk shell nacre framework layer may actually consist of several framework hydrogelator proteins, such as n16.3, which can promote mineral nanoparticle organization and assembly during the nacre biomineralization process and also serve as a model system for designing ion-responsive, composite, and smart hydrogels.« less

Room-temperature fabrication of core-shell nano-ZnO/pollen grain biocomposite for adsorptive removal of organic dye from water

NASA Astrophysics Data System (ADS)

Tzvetkov, George; Kaneva, Nina; Spassov, Tony

2017-04-01

A new core-shell nano-ZnO/pollen grain (n-ZnO/PG) biocomposite has been successfully synthesized via simple and low-temperature two-step liquid precipitation method. The synthetic strategy consists of grafting the surface of pine pollen grains (PG) with Zn2+-organic complexes followed by a treatment in Zn(CH3COO)2/NaOH solution, thus producing a closed n-ZnO shell around the organic core, with a thickness of ∼450 nm. Scanning electron microscopy, X-ray diffraction, FTIR, XPS and UV-vis spectroscopy measurements along with N2 adsorption/desorption were used to characterize the resulting n-ZnO/PG biocomposite. The as-prepared core-shell microparticles are meso-/macro-porous with BET surface area of 25 m2 g-1 and total pore volume of 0.26 cm3 g-1. The adsorption properties of n-ZnO/PG were evaluated through adsorption of Malachite Green (MG) from aqueous medium at room temperature (25 °C). For the sake of comparison, the physico-chemical and adsorptive properties of the raw PG and pure n-ZnO were also examined. Results indicate that n-ZnO/PG is the most favorable for the adsorption of MG under the conditions used in this study. The adsorption kinetic data for PG, n-ZnO and n-ZnO/PG follow the pseudo-second order equation and the maximum adsorption capacity follows an order of n-ZnO/PG > n-ZnO > PG. For n-ZnO/PG an adsorption uptake up to 145.9 mg g-1 is observed. The as-prepared core-shell biocomposite material is a promising cost-effective and environmentally friendly adsorbent due to its textural properties, surface chemistry, adsorption capacity and recyclability.

Sensitivity towards elevated pCO2 in great scallop (Pecten maximus Lamarck) embryos and fed larvae

NASA Astrophysics Data System (ADS)

Andersen, Sissel; Grefsrud, Ellen S.; Harboe, Torstein

2017-02-01

The increasing amount of dissolved anthropogenic CO2 has caused a drop in pH values in the open ocean known as ocean acidification. This change in seawater carbonate chemistry has been shown to have a negative effect on a number of marine organisms. Early life stages are the most vulnerable, and especially the organisms that produce calcified structures in the phylum Mollusca. Few studies have looked at effects on scallops, and this is the first study presented including fed larvae of the great scallop (Pecten maximus) followed until day 14 post-fertilization. Fertilized eggs from unexposed parents were exposed to three levels of pCO2 using four replicate units: 465 (ambient), 768 and 1294 µatm, corresponding to pHNIST of 7.94, 7.75 (-0.19 units) and 7.54 (-0.40 units), respectively. All of the observed parameters were negatively affected by elevated pCO2: survival, larval development, shell growth and normal shell development. The latter was observed to be affected only 2 days after fertilization. Negative effects on the fed larvae at day 7 were similar to what was shown earlier for unfed P. maximus larvae. Growth rate in the group at 768 µatm seemed to decline after day 7, indicating that the ability to overcome the environmental change at moderately elevated pCO2 was lost over time. The present study shows that food availability does not decrease the sensitivity to elevated pCO2 in P. maximus larvae. Unless genetic adaptation and acclimatization counteract the negative effects of long term elevated pCO2, recruitment in populations of P. maximus will most likely be negatively affected by the projected drop of 0.06-0.32 units in pH within year 2100.

Does Height to Width Ratio Correlate with Mean Volume in Gastropods?

NASA Astrophysics Data System (ADS)

Barriga, R.; Seixas, G.; Payne, J.

2012-12-01

Marine organisms' shell shape and size show important biological information. For example, shape and size can dictate how the organism ranges for food and escapes predation. Due to lack of data and analysis, the evolution of shell size in marine gastropods (snails) remains poorly known. In this study, I attempt to find the relationship between height to width ratio and mean volume. I collected height and width measurements from primary literature sources and calculated volume from these measurements. My results indicate that there was no correlation between height to width ratio and mean volume between 500 to 200 Ma, but there was a correlation between 200 Ma to present where there is a steady increase in both height to width ratio and mean volume. This means that shell shape was not an important factor at the beginning of gastropod evolution but after 200 Ma body size evolution was increasingly driven by the height to width ratio.

Engineering the Bacterial Microcompartment Domain for Molecular Scaffolding Applications

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

Young, Eric J.; Burton, Rodney; Mahalik, Jyoti P.

As synthetic biology advances the intricacy of engineered biological systems, the importance of spatial organization within the cellular environment must not be marginalized. Increasingly, biological engineers are investigating means to control spatial organization within the cell, mimicking strategies used by natural pathways to increase flux and reduce cross-talk. A modular platform for constructing a diverse set of defined, programmable architectures would greatly assist in improving yields from introduced metabolic pathways and increasing insulation of other heterologous systems. Here, we review recent research on the shell proteins of bacterial microcompartments and discuss their potential application as “building blocks” for a rangemore » of customized intracellular scaffolds. As a result, we summarize the state of knowledge on the self-assembly of BMC shell proteins and discuss future avenues of research that will be important to realize the potential of BMC shell proteins as predictively assembling and programmable biological materials for bioengineering.« less

Engineering the Bacterial Microcompartment Domain for Molecular Scaffolding Applications

DOE PAGES

Young, Eric J.; Burton, Rodney; Mahalik, Jyoti P.; ...

2017-07-31

As synthetic biology advances the intricacy of engineered biological systems, the importance of spatial organization within the cellular environment must not be marginalized. Increasingly, biological engineers are investigating means to control spatial organization within the cell, mimicking strategies used by natural pathways to increase flux and reduce cross-talk. A modular platform for constructing a diverse set of defined, programmable architectures would greatly assist in improving yields from introduced metabolic pathways and increasing insulation of other heterologous systems. Here, we review recent research on the shell proteins of bacterial microcompartments and discuss their potential application as “building blocks” for a rangemore » of customized intracellular scaffolds. As a result, we summarize the state of knowledge on the self-assembly of BMC shell proteins and discuss future avenues of research that will be important to realize the potential of BMC shell proteins as predictively assembling and programmable biological materials for bioengineering.« less

Engineering the Bacterial Microcompartment Domain for Molecular Scaffolding Applications

PubMed Central

Young, Eric J.; Burton, Rodney; Mahalik, Jyoti P.; Sumpter, Bobby G.; Fuentes-Cabrera, Miguel; Kerfeld, Cheryl A.; Ducat, Daniel C.

2017-01-01

As synthetic biology advances the intricacy of engineered biological systems, the importance of spatial organization within the cellular environment must not be marginalized. Increasingly, biological engineers are investigating means to control spatial organization within the cell, mimicking strategies used by natural pathways to increase flux and reduce cross-talk. A modular platform for constructing a diverse set of defined, programmable architectures would greatly assist in improving yields from introduced metabolic pathways and increasing insulation of other heterologous systems. Here, we review recent research on the shell proteins of bacterial microcompartments and discuss their potential application as “building blocks” for a range of customized intracellular scaffolds. We summarize the state of knowledge on the self-assembly of BMC shell proteins and discuss future avenues of research that will be important to realize the potential of BMC shell proteins as predictively assembling and programmable biological materials for bioengineering. PMID:28824573

External and internal shell formation in the ramshorn snail Marisa cornuarietis are extremes in a continuum of gradual variation in development

PubMed Central

2013-01-01

Background Toxic substances like heavy metals can inhibit and disrupt the normal embryonic development of organisms. Exposure to platinum during embryogenesis has been shown to lead to a “one fell swoop” internalization of the shell in the ramshorn snail Marisa cornuarietis, an event which has been discussed to be possibly indicative of processes in evolution which may result in dramatic changes in body plans. Results Whereas at usual cultivation temperature, 26°C, platinum inhibits the growth of both shell gland and mantle edge during embryogenesis leading to an internalization of the mantle and, thus, also of the shell, higher temperatures induce a re-start of the differential growth of the mantle edge and the shell gland after a period of inactivity. Here, developing embryos exhibit a broad spectrum of shell forms: in some individuals only the ventral part of the visceral sac is covered while others develop almost “normal” shells. Histological studies and scanning electron microscopy images revealed platinum to inhibit the differential growth of the shell gland and the mantle edge, and elevated temperature (28 - 30°C) to mitigate this platinum effect with varying efficiency. Conclusion We could show that the formation of internal, external, and intermediate shells is realized within the continuum of a developmental gradient defined by the degree of differential growth of the embryonic mantle edge and shell gland. The artificially induced internal and intermediate shells are first external and then partly internalized, similar to internal shells found in other molluscan groups. PMID:23682742

An Analysis of the Computer Security Ramifications of Weakened Asymmetric Cryptographic Algorithms

DTIC Science & Technology

2012-06-01

OpenVPN (Yonan). TLS (and by extension SSL) obviously rely on encryption to provide the confidentiality, integrity and authentication services it...Secure Shell (SSH) Transport Layer Protocol.” IETF, Jan. 2006. <tools.ietf.org/html/rfc4253> Yonan, James, and Mattock. " OpenVPN ." SourceForge...11 May 2012. <http://sourceforge.net/projects/ openvpn /> 92 REPORT DOCUMENTATION PAGE Form Approved OMB No. 074-0188 The public reporting

Minute co-variations of Sr/Ca ratios and microstructures in the aragonitic shell of Cerastoderma edule (Bivalvia) - Are geochemical variations at the ultra-scale masking potential environmental signals?

NASA Astrophysics Data System (ADS)

Füllenbach, Christoph S.; Schöne, Bernd R.; Shirai, Kotaro; Takahata, Naoto; Ishida, Akizumi; Sano, Yuji

2017-05-01

It remains a challenging task to reconstruct water temperatures from Sr/Ca ratios of bivalve shells. Although in many aragonitic species, Sr/Ca is negatively correlated to temperature - which is expected based on abiogenic precipitation experiments, the incorporation of Sr into the shell of bivalves is strongly controlled by physiological processes and occurs away from the predicted thermodynamic equilibrium. Strontium-to-calcium ratios of aragonitic shells remain far below that of the ambient water. Moreover, Sr concentrations vary considerably among shell portions consisting of different microstructures and/or organic content. Values observed at annual growth lines and within the intervening shell portions (= annual growth increments) deviate much stronger from each other than expected from a change in temperature or Sr/Cawater. As demonstrated here by ultra-high-resolution chemical analysis (EPMA, NanoSIMS) of a Cerastoderma edule shell, Sr concentrations are also heterogeneously distributed at approximately micrometer resolution. For example, in the outer portion of the outer shell layer, Sr/Ca ratios were statistically significantly (t-, u-tests) higher at circatidal growth lines (irregular simple prismatic structure; arithmetic mean ± 1 standard deviation = 2.86 ± 0.38 mmol/mol; n = 53) than within circatidal increments (nondenticular prismatic structure; 2.42 ± 0.25 mmol/mol; n = 51). S/Cashell, a representative of the concentration of organics, showed the opposite pattern, i.e., significantly higher values in circatidal increments (2.37 ± 0.29 mmol/mol; n = 51) than at circatidal growth lines (2.13 ± 0.47 mmol/mol; n = 53). Overall highest values of Sr/Cashell (3.47 ± 0.65 mmol/mol; n = 3) and S/Cashell (3.98 ± 0.65 mmol/mol; n = 3), however, were typically associated with annual growth lines and larger biomineral units. The intimate link between Sr/Cashell, S/Cashell and shell architecture may indicate that microstructures or the processes controlling their formation exert a strong control over the incorporation of strontium into shells of C. edule. Analytical techniques with lower sampling resolution, e.g., LA-ICP-MS, cannot resolve such fine-scale Sr variations. As a result, the signal-to-noise ratio decreases and the data generated by such techniques may therefore not seem to provide useful paleotemperature data. Future studies should therefore employ a combined analysis of Sr/Cashell and shell microstructures, and interpret Sr/Ca values of shell portions with different microstructures separately.

Low temperature grown ZnO@TiO{sub 2} core shell nanorod arrays for dye sensitized solar cell application

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

Goh, Gregory Kia Liang; Le, Hong Quang, E-mail: lehq@imre.a-star.edu.sg; Huang, Tang Jiao

High aspect ratio ZnO nanorod arrays were synthesized on fluorine-doped tin oxide glasses via a low temperature solution method. By adjusting the growth condition and adding polyethylenimine, ZnO nanorod arrays with tunable length were successfully achieved. The ZnO@TiO{sub 2} core shells structures were realized by a fast growth method of immersion into a (NH{sub 4}){sub 2}·TiF{sub 6} solution. Transmission electron microscopy, X-ray Diffraction and energy dispersive X-ray measurements all confirmed the existence of a titania shell uniformly covering the ZnO nanorod's surface. Results of solar cell testing showed that addition of a TiO{sub 2} shell to the ZnO nanorod significantlymore » increased short circuit current (from 4.2 to 5.2 mA/cm{sup 2}), open circuit voltage (from 0.6 V to 0.8 V) and fill factor (from 42.8% to 73.02%). The overall cell efficiency jumped from 1.1% for bare ZnO nanorod to 3.03% for a ZnO@TiO{sub 2} core shell structured solar cell with a 18–22 nm shell thickness, a nearly threefold increase. - Graphical abstract: The synthesis process of coating TiO{sub 2} shell onto ZnO nanorod core is shown schematically. A thin, uniform, and conformal shell had been grown on the surface of the ZnO core after immersing in the (NH{sub 4}){sub 2}·TiF{sub 6} solution for 5–15 min. - Highlights: • ZnO@TiO{sub 2} core shell nanorod has been grown on FTO substrate using low temperature solution method. • TEM, XRD, EDX results confirmed the existing of titana shell, uniformly covered rod's surface. • TiO{sub 2} shell suppressed recombination, demonstrated significant enhancement in cell's efficiency. • Core shell DSSC's efficiency achieved as high as 3.03%, 3 times higher than that of ZnO nanorods.« less

The effect of ring distortions on buckling of blunt conical shells. [Viking mission aeroshell

NASA Technical Reports Server (NTRS)

Heard, W. L., Jr.; Anderson, M. S.; Stephens, W. B.

1975-01-01

A rigorous analytical study of cones stiffened by many thin-gage, open-section rings is presented. The results are compared with data previously obtained from uniform pressure tests of the Viking mission flight aeroshell and of the Viking structural prototype aeroshells. A conventional analysis, in which the rings are modeled as discrete rigid cross sections, is shown to lead to large, unconservative strength predictions. A more sophisticated technique of modeling the rings as shell branches leads to much more realistic strength predictions and more accurately predicts the failure modes. It is also shown that if a small initial imperfection proportional to the shape of the buckling mode is assumed, the critical buckling modes from analysis and test are in agreement. However, the reduction in buckling strength from the perfect-shell predictions is small.

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.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Water-soluble core/shell nanoparticles for proton therapy through particle-induced radiation

NASA Astrophysics Data System (ADS)

Park, Jeong Chan; Jung, Myung-Hwan; Kim, Maeng Jun; Kim, Kye-Ryung

2015-02-01

Metallic nanoparticles have been used in biomedical applications such as magnetic resonance imaging (MRI), therapy, and drug delivery systems. Metallic nanoparticles as therapeutic tools have been demonstrated using radio-frequency magnetic fields or near-infrared light. Recently, therapeutic applications of metallic nanomaterials combined with proton beams have been reported. Particle-induced radiation from metallic nanoparticles, which can enhance the therapeutic effects of proton therapy, was released when the nanoparticles were bombarded by a high-energy proton beam. Core/shell nanoparticles, especially Au-coated magnetic nanoparticles, have drawn attention in biological applications due to their attractive characteristics. However, studies on the phase transfer of organic-ligand-based core/shell nanoparticles into water are limited. Herein, we demonstrated that hydrophobic core/shell structured nanomaterials could be successfully dispersed in water through chloroform/surfactant mixtures. The effects of the core/shell nanomaterials and the proton irradiation on Escherichia coli (E. coli) were also explored.

Use of extracts from oyster shell and soil for cultivation of Spirulina maxima.

PubMed

Jung, Joo-Young; Kim, Sunmin; Lee, Hansol; Kim, Kyochan; Kim, Woong; Park, Min S; Kwon, Jong-Hee; Yang, Ji-Won

2014-12-01

Calcium ion and trace metals play important roles in various metabolisms of photosynthetic organisms. In this study, simple methods were developed to extract calcium ion and micronutrients from oyster shell and common soil, and the prepared extracts were tested as a replacement of the corresponding chemicals that are essential for growth of microalgae. The oyster shell and soil were treated with 0.1 M sodium hydroxide or with 10 % hydrogen peroxide, respectively. The potential application of these natural sources to cultivation was investigated with Spirulina maxima. When compared to standard Zarrouk medium, the Spirulina maxima cultivated in a modified Zarrouk media with elements from oyster shell and soil extract exhibited increases in biomass, chlorophyll, and phycocyanin by 17, 16, and 64 %, respectively. These results indicate that the extracts of oyster shell and soil provide sufficient amounts of calcium and trace metals for successful cultivation of Spirulina maxima.

Cocoa Shell: A By-Product with Great Potential for Wide Application.

PubMed

Panak Balentić, Jelena; Ačkar, Đurđica; Jokić, Stela; Jozinović, Antun; Babić, Jurislav; Miličević, Borislav; Šubarić, Drago; Pavlović, Nika

2018-06-09

Solving the problem of large quantities of organic waste, which represents an enormous ecological and financial burden for all aspects of the process industry, is a necessity. Therefore, there is an emerged need to find specific solutions to utilize raw materials as efficiently as possible in the production process. The cocoa shell is a valuable by-product obtained from the chocolate industry. It is rich in protein, dietary fiber, and ash, as well as in some other valuable bioactive compounds, such as methylxanthines and phenolics. This paper gives an overview of published results related to the cocoa shell, mostly on important bioactive compounds and possible applications of the cocoa shell in different areas. The cocoa shell, due to its nutritional value and high-value bioactive compounds, could become a desirable raw material in a large spectrum of functional, pharmaceutical, or cosmetic products, as well as in the production of energy or biofuels in the near future.

Effects of gold diffusion on n-type doping of GaAs nanowires.

PubMed

Tambe, Michael J; Ren, Shenqiang; Gradecak, Silvija

2010-11-10

The deposition of n-GaAs shells is explored as a method of n-type doping in GaAs nanowires grown by the Au-mediated metal-organic chemical vapor deposition. Core-shell GaAs/n-GaAs nanowires exhibit an unintended rectifying behavior that is attributed to the Au diffusion during the shell deposition based on studies using energy dispersive X-ray spectroscopy, current-voltage, capacitance-voltage, and Kelvin probe force measurements. Removing the gold prior to n-type shell deposition results in the realization of n-type GaAs nanowires without rectification. We directly correlate the presence of gold impurities to nanowire electrical properties and provide an insight into the role of seed particles on the properties of nanowires and nanowire heterostructures.

The shells of BMC-type microcompartment organelles in bacteria.

PubMed

Yeates, Todd O; Jorda, Julien; Bobik, Thomas A

2013-01-01

Bacterial microcompartments are large proteinaceous structures that act as metabolic organelles in many bacterial cells. A shell or capsid, which is composed of a few thousand protein subunits, surrounds a series of sequentially acting enzymes and controls the diffusion of substrates and products into and out of the lumen. The carboxysome and the propanediol utilization microcompartment represent two well-studied systems among seven or more distinct types that can be delineated presently. Recent structural studies have highlighted a number of sophisticated mechanisms that underlie the function of bacterial microcompartment shell proteins. This review updates our understanding of bacterial microcompartment shells, how they are assembled, and how they carry out their functions in molecular transport and enzyme organization. Copyright © 2013 S. Karger AG, Basel.

Dependence of weak interaction rates on the nuclear composition during stellar core collapse

NASA Astrophysics Data System (ADS)

Furusawa, Shun; Nagakura, Hiroki; Sumiyoshi, Kohsuke; Kato, Chinami; Yamada, Shoichi

2017-02-01

We investigate the influences of the nuclear composition on the weak interaction rates of heavy nuclei during the core collapse of massive stars. The nuclear abundances in nuclear statistical equilibrium (NSE) are calculated by some equation of state (EOS) models including in-medium effects on nuclear masses. We systematically examine the sensitivities of electron capture and neutrino-nucleus scattering on heavy nuclei to the nuclear shell effects and the single-nucleus approximation. We find that the washout of the shell effect at high temperatures brings significant change to weak rates by smoothing the nuclear abundance distribution: the electron capture rate decreases by ˜20 % in the early phase and increases by ˜40 % in the late phase at most, while the cross section for neutrino-nucleus scattering is reduced by ˜15 % . This is because the open-shell nuclei become abundant instead of those with closed neutron shells as the shell effects disappear. We also find that the single-nucleus description based on the average values leads to underestimations of weak rates. Electron captures and neutrino coherent scattering on heavy nuclei are reduced by ˜80 % in the early phase and by ˜5 % in the late phase, respectively. These results indicate that NSE like EOS accounting for shell washout is indispensable for the reliable estimation of weak interaction rates in simulations of core-collapse supernovae.

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.

Au@Ag core-shell nanocubes for efficient plasmonic light scattering effect in low bandgap organic solar cells.

PubMed

Baek, Se-Woong; Park, Garam; Noh, Jonghyeon; Cho, Changsoon; Lee, Chun-Ho; Seo, Min-Kyo; Song, Hyunjoon; Lee, Jung-Yong

2014-04-22

In this report, we propose a metal-metal core-shell nanocube (NC) as an advanced plasmonic material for highly efficient organic solar cells (OSCs). We covered an Au core with a thin Ag shell as a scattering enhancer to build Au@Ag NCs, which showed stronger scattering efficiency than Au nanoparticles (AuNPs) throughout the visible range. Highly efficient plasmonic organic solar cells were fabricated by embedding Au@Ag NCs into an anodic buffer layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and the power conversion efficiency was enhanced to 6.3% from 5.3% in poly[N-9-hepta-decanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)] (PCDTBT):[6,6]-phenyl C71-butyric acid methyl ester (PC70BM) based OSCs and 9.2% from 7.9% in polythieno[3,4-b]thiophene/benzodithiophene (PTB7):PC70BM based OSCs. The Au@Ag NC plasmonic PCDTBT:PC70BM-based organic solar cells showed 2.2-fold higher external quantum efficiency enhancement compared to AuNPs devices at a wavelength of 450-700 nm due to the amplified plasmonic scattering effect. Finally, we proved the strongly enhanced plasmonic scattering efficiency of Au@Ag NCs embedded in organic solar cells via theoretical calculations and detailed optical measurements.

Portable tomographic PIV measurements of swimming shelled Antarctic pteropods

NASA Astrophysics Data System (ADS)

Adhikari, Deepak; Webster, Donald R.; Yen, Jeannette

2016-12-01

A portable tomographic particle image velocimetry (tomographic PIV) system is described. The system was successfully deployed in Antarctica to study shelled Antarctic pteropods ( Limacina helicina antarctica)—a delicate organism with an unusual propulsion mechanism. The experimental setup consists of a free-standing frame assembled with optical rails, thus avoiding the need for heavy and bulky equipment (e.g. an optical table). The cameras, lasers, optics, and tanks are all rigidly supported within the frame assembly. The results indicate that the pteropods flap their parapodia (or "wings") downward during both power and recovery strokes, which is facilitated by the pitching of their shell. Shell pitching significantly alters the flapping trajectory, allowing the pteropod to move vertically and/or horizontally. The pronation and supination of the parapodia, together with the figure-eight motion during flapping, suggest similarities with insect flight. The volumetric velocity field surrounding the freely swimming pteropod reveals the generation of an attached vortex ring connecting the leading-edge vortex to the trailing-edge vortex during power stroke and a presence of a leading-edge vortex during recovery stroke. These vortex structures play a major role in accelerating the organism vertically and indicate that forces generated on the parapodia during flapping constitute both lift and drag. After completing each stroke, two vortex rings are shed into the wake of the pteropod. The complex combination of body kinematics (parapodia flapping, shell pitch, sawtooth trajectory), flow structures, and resulting force balance may be significantly altered by thinning of the pteropod shell, thus making pteropods an indicator of the detrimental effects of ocean acidification.

Ocean acidification reduces the crystallographic control in juvenile mussel shells.

PubMed

Fitzer, Susan C; Cusack, Maggie; Phoenix, Vernon R; Kamenos, Nicholas A

2014-10-01

Global climate change threatens the oceans as anthropogenic carbon dioxide causes ocean acidification and reduced carbonate saturation. Future projections indicate under saturation of aragonite, and potentially calcite, in the oceans by 2100. Calcifying organisms are those most at risk from such ocean acidification, as carbonate is vital in the biomineralisation of their calcium carbonate protective shells. This study highlights the importance of multi-generational studies to investigate how marine organisms can potentially adapt to future projected global climate change. Mytilus edulis is an economically important marine calcifier vulnerable to decreasing carbonate saturation as their shells comprise two calcium carbonate polymorphs: aragonite and calcite. M. edulis specimens were cultured under current and projected pCO2 (380, 550, 750 and 1000μatm), following 6months of experimental culture, adults produced second generation juvenile mussels. Juvenile mussel shells were examined for structural and crystallographic orientation of aragonite and calcite. At 1000μatm pCO2, juvenile mussels spawned and grown under this high pCO2 do not produce aragonite which is more vulnerable to carbonate under-saturation than calcite. Calcite and aragonite were produced at 380, 550 and 750μatm pCO2. Electron back scatter diffraction analyses reveal less constraint in crystallographic orientation with increased pCO2. Shell formation is maintained, although the nacre crystals appear corroded and crystals are not so closely layered together. The differences in ultrastructure and crystallography in shells formed by juveniles spawned from adults in high pCO2 conditions may prove instrumental in their ability to survive ocean acidification. Copyright © 2014 Elsevier Inc. All rights reserved.

δ15N as a proxy for historic anthropogenic nitrogen loading in Charleston Harbor, SC, USA

NASA Astrophysics Data System (ADS)

Payne, T. N.; Andrus, C. F. T.

2015-12-01

Bivalve shell geochemistry can serve as a useful indicator of changes in coastal environments. There is increasing interest in developing paleoenvironmental proxies from mollusk shell organic components. Numerous studies have focused on how the δ15N obtained from bivalve tissues can be used to trace present-day wastewater input into estuaries. However, comparatively little attention has been paid to tracing the impact of anthropogenic nitrogen loading into estuaries over time. By measuring historic levels of δ15N in the organic fraction of oyster shells (Crassostrea virginica) from archaeological sites around Charleston Harbor and comparing those levels to the δ15N content of modern shells, it is possible to assess how nitrogen has fluctuated historically in the area. Whole-shell samples from the Late Archaic Period (~3000-4000 BP, Late Woodland Period (~1400-800 BP), 18th and 19th centuries, and modern controls were measured for %N and d15N. Evidence of increased anthropogenic input of N is expected to begin in the early historic period based on similar analysis in Chesapeake Bay. More ancient samples may give insight into baseline conditions prior to recent population growth and industrialization. This information could help understand how large-scale anthropogenic nitrogen loading has affected coastal ecosystems over time and guide future remediation. Furthermore, this project will help refine and improve this novel proxy of past environmental conditions.

An Enzyme-Coated Metal-Organic Framework Shell for Synthetically Adaptive Cell Survival.

PubMed

Liang, Kang; Richardson, Joseph J; Doonan, Christian J; Mulet, Xavier; Ju, Yi; Cui, Jiwei; Caruso, Frank; Falcaro, Paolo

2017-07-10

A bioactive synthetic porous shell was engineered to enable cells to survive in an oligotrophic environment. Eukaryotic cells (yeast) were firstly coated with a β-galactosidase (β-gal), before crystallization of a metal-organic framework (MOF) film on the enzyme coating; thereby producing a bioactive porous synthetic shell. The β-gal was an essential component of the bioactive shell as it generated nutrients (that is, glucose and galactose) required for cell viability in nutrient-deficient media (lactose-based). Additionally, the porous MOF coating carried out other vital functions, such as 1) shielding the cells from cytotoxic compounds and radiation, 2) protecting the non-native enzymes (β-gal in this instance) from degradation and internalization, and 3) allowing for the diffusion of molecules essential for the survival of the cells. Indeed, this bioactive porous shell enabled the survival of cells in simulated extreme oligotrophic environments for more than 7 days, leading to a decrease in cell viability less than 30 %, versus a 99 % decrease for naked yeast. When returned to optimal growth conditions the bioactive porous exoskeleton could be removed and the cells regained full growth immediately. The construction of bioactive coatings represents a conceptually new and promising approach for the next-generation of cell-based research and application, and is an alternative to synthetic biology or genetic modification. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Variation in Orthologous Shell-Forming Proteins Contribute to Molluscan Shell Diversity.

PubMed

Jackson, Daniel J; Reim, Laurin; Randow, Clemens; Cerveau, Nicolas; Degnan, Bernard M; Fleck, Claudia

2017-11-01

Despite the evolutionary success and ancient heritage of the molluscan shell, little is known about the molecular details of its formation, evolutionary origins, or the interactions between the material properties of the shell and its organic constituents. In contrast to this dearth of information, a growing collection of molluscan shell-forming proteomes and transcriptomes suggest they are comprised of both deeply conserved, and lineage specific elements. Analyses of these sequence data sets have suggested that mechanisms such as exon shuffling, gene co-option, and gene family expansion facilitated the rapid evolution of shell-forming proteomes and supported the diversification of this phylum specific structure. In order to further investigate and test these ideas we have examined the molecular features and spatial expression patterns of two shell-forming genes (Lustrin and ML1A2) and coupled these observations with materials properties measurements of shells from a group of closely related gastropods (abalone). We find that the prominent "GS" domain of Lustrin, a domain believed to confer elastomeric properties to the shell, varies significantly in length between the species we investigated. Furthermore, the spatial expression patterns of Lustrin and ML1A2 also vary significantly between species, suggesting that both protein architecture, and the regulation of spatial gene expression patterns, are important drivers of molluscan shell evolution. Variation in these molecular features might relate to certain materials properties of the shells of these species. These insights reveal an important and underappreciated source of variation within shell-forming proteomes that must contribute to the diversity of molluscan shell phenotypes. © The Author 2017. Published by Oxford University Press on behalf of the Society for Molecular Biology and Evolution.

Thermal invisibility based on scattering cancellation and mantle cloaking

PubMed Central

Farhat, M.; Chen, P.-Y.; Bagci, H.; Amra, C.; Guenneau, S.; Alù, A.

2015-01-01

We theoretically and numerically analyze thermal invisibility based on the concept of scattering cancellation and mantle cloaking. We show that a small object can be made completely invisible to heat diffusion waves, by tailoring the heat conductivity of the spherical shell enclosing the object. This means that the thermal scattering from the object is suppressed, and the heat flow outside the object and the cloak made of these spherical shells behaves as if the object is not present. Thermal invisibility may open new vistas in hiding hot spots in infrared thermography, military furtivity, and electronics heating reduction. PMID:25928664

The connectome viewer toolkit: an open source framework to manage, analyze, and visualize connectomes.

PubMed

Gerhard, Stephan; Daducci, Alessandro; Lemkaddem, Alia; Meuli, Reto; Thiran, Jean-Philippe; Hagmann, Patric

2011-01-01

Advanced neuroinformatics tools are required for methods of connectome mapping, analysis, and visualization. The inherent multi-modality of connectome datasets poses new challenges for data organization, integration, and sharing. We have designed and implemented the Connectome Viewer Toolkit - a set of free and extensible open source neuroimaging tools written in Python. The key components of the toolkit are as follows: (1) The Connectome File Format is an XML-based container format to standardize multi-modal data integration and structured metadata annotation. (2) The Connectome File Format Library enables management and sharing of connectome files. (3) The Connectome Viewer is an integrated research and development environment for visualization and analysis of multi-modal connectome data. The Connectome Viewer's plugin architecture supports extensions with network analysis packages and an interactive scripting shell, to enable easy development and community contributions. Integration with tools from the scientific Python community allows the leveraging of numerous existing libraries for powerful connectome data mining, exploration, and comparison. We demonstrate the applicability of the Connectome Viewer Toolkit using Diffusion MRI datasets processed by the Connectome Mapper. The Connectome Viewer Toolkit is available from http://www.cmtk.org/

Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

NASA Astrophysics Data System (ADS)

Mukherjee, Sanjoy; Boudouris, Bryan

The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

The Connectome Viewer Toolkit: An Open Source Framework to Manage, Analyze, and Visualize Connectomes

PubMed Central

Gerhard, Stephan; Daducci, Alessandro; Lemkaddem, Alia; Meuli, Reto; Thiran, Jean-Philippe; Hagmann, Patric

2011-01-01

Advanced neuroinformatics tools are required for methods of connectome mapping, analysis, and visualization. The inherent multi-modality of connectome datasets poses new challenges for data organization, integration, and sharing. We have designed and implemented the Connectome Viewer Toolkit – a set of free and extensible open source neuroimaging tools written in Python. The key components of the toolkit are as follows: (1) The Connectome File Format is an XML-based container format to standardize multi-modal data integration and structured metadata annotation. (2) The Connectome File Format Library enables management and sharing of connectome files. (3) The Connectome Viewer is an integrated research and development environment for visualization and analysis of multi-modal connectome data. The Connectome Viewer's plugin architecture supports extensions with network analysis packages and an interactive scripting shell, to enable easy development and community contributions. Integration with tools from the scientific Python community allows the leveraging of numerous existing libraries for powerful connectome data mining, exploration, and comparison. We demonstrate the applicability of the Connectome Viewer Toolkit using Diffusion MRI datasets processed by the Connectome Mapper. The Connectome Viewer Toolkit is available from http://www.cmtk.org/ PMID:21713110

Self-Assembled Core-Shell CdTe/Poly(3-hexylthiophene) Nanoensembles as Novel Donor-Acceptor Light-Harvesting Systems.

PubMed

Istif, Emin; Kagkoura, Antonia; Hernandez-Ferrer, Javier; Stergiou, Anastasios; Skaltsas, Theodosis; Arenal, Raul; Benito, Ana M; Maser, Wolfgang K; Tagmatarchis, Nikos

2017-12-27

The self-assembly of novel core-shell nanoensembles consisting of regioregular poly(3-hexylthiophene) nanoparticles (P3HT NPs ) of 100 nm as core and semiconducting CdTe quantum dots (CdTe QDs ) as shell with a thickness of a few tens of nanometers was accomplished by employing a reprecipitation approach. The structure, morphology, and composition of CdTe QDs /P3HT NPs nanoensembles were confirmed by high-resolution scanning transmission microscopy and dynamic light-scattering studies. Intimate interface contact between the CdTe QDs shell and the P3HT NPs core leads to the stabilization of the CdTe QDs /P3HT NPs nanoensemble as probed by the steady-state absorption spectroscopy. Effective quenching of the characteristic photoluminescence of CdTe QDs at 555 nm, accompanied by simultaneous increase in emission of P3HT NPs at 660 and 720 nm, reveals photoinduced charge-transfer processes. Probing the redox properties of films of CdTe QDs /P3HT NPs further proves the formation of a stabilized core-shell system in the solid state. Photoelectrochemical assays on CdTe QDs /P3HT NPs films show a reversible on-off photoresponse at a bias voltage of +0.8 V with a 3 times increased photocurrent compared to CdTe QDs . The improved charge separation is directly related to the unique core-shell configuration, in which the outer CdTe QDs shell forces the P3HT NPs core to effectively act as electron acceptor. The creation of novel donor-acceptor core-shell hybrid materials via self-assembly is transferable to other types of conjugated polymers and semiconducting nanoparticles. This work, therefore, opens new pathways for the design of improved optoelectronic devices.

Ecophenotypic plasticity leads to extraordinary gastropod shells found on the “Roof of the World”

PubMed Central

Clewing, Catharina; Riedel, Frank; Wilke, Thomas; Albrecht, Christian

2015-01-01

The often extraordinary shell forms and shapes of gastropods found in palaeolakes, such as the highly diverse Gyraulus fauna of the famous Steinheim Basin, have been puzzling evolutionary biologists for centuries, and there is an ongoing debate whether these aberrant shell forms are indicative of true species (or subspecies) or ecophenotypic morphs. Interestingly, one of the Steinheim Gyraulus morphs – a corkscrew-like open-coiled shell – has a recent analogue in the Lake Bangong drainage system on the western Tibetan Plateau. Therefore, a combination of morphological, molecular, palaeolimnological, and ecological analyses was used in this study to assess whether the extraordinary shell shape in Gyraulus sp. from this drainage system represents a (young) ecophenotypic phenomenon or if it has been genetically fixed over an extended period of time. Our morphological, ecological, and palaeolimnological data suggest that the corkscrew-like specimens remain restricted to a small pond near Lake Bangong with an elevated pH value and that the colonization may have occurred recently. The phylogenetic reconstruction based on two gene fragments shows that these nonplanispiral specimens cluster within the previous described Tibetan Plateau Gyraulus clade N2. A network analysis indicates that some haplotypes are even shared by planispiral and nonplanispiral specimens. Given the ephemerality of the phenomenon, the compact network patterns inferred, the likely young phylogenetic age of the aberrant Gyraulus shells studied, and the ecological peculiarities of the study site, we suggest that the evolution of the aberrant shell forms on the Tibetan Plateau could likely be considered as a rapid ecophenotypic response, possibly induced by ecological stress. This finding may thus have implications for the ongoing debate about the processes that have caused the extraordinary shell diversity in palaeolakes such as the Steinheim Basin. PMID:26306180

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

Wang Shumin; Tian Hongwei; Pei Yanhui

A novel hedgehog-like core/shell structure, consisting of a high density of vertically aligned graphene sheets and a thin graphene shell/a copper core (VGs-GS/CC), has been synthesized via a simple one-step synthesis route using radio-frequency plasma-enhanced chemical vapor deposition (RF-PECVD). Scanning and transmission electron microscopy investigations show that the morphology of this core/shell material could be controlled by deposition time. For a short deposition time, only multilayer graphene shell tightly surrounds the copper particle, while as the deposition time is relative long, graphene sheets extend from the surface of GS/CC. The GS can protect CC particles from oxidation. The growth mechanismmore » for the obtained GS/CC and VGs-GS/CC has been revealed. Compared to VGs, VGs-GS/CC material exhibits a better electron field emission property. This investigation opens a possibility for designing a core/shell structure of different carbon-metal hybrid materials for a wide variety of practical applications. - Graphical abstract: With increasing deposition time, graphene sheets extend from the surface of GS/CC, causing the multilayer graphene encapsulated copper to be converted into vertically aligned graphene sheets-graphene shell/copper core structure. Highlights: Black-Right-Pointing-Pointer A novel hedgehog-like core/shell structure has been synthesized. Black-Right-Pointing-Pointer The structure consists of vertical graphene sheets-graphene shell and copper core. Black-Right-Pointing-Pointer The morphology of VGs-GS/CC can be controlled by choosing a proper deposition time. Black-Right-Pointing-Pointer With increasing deposition time, graphene sheets extend from the surface of GS/CC. Black-Right-Pointing-Pointer VGs-GS/CC exhibits a better electron field emission property as compared with VGs.« less

Crystal and Solution Structures of a Prokaryotic M16B Peptidase: an Open and Shut Case

PubMed Central

Aleshin, Alexander E.; Gramatikova, Svetlana; Hura, Gregory L.; Bobkov, Andrey; Strongin, Alex Y.; Stec, Boguslaw; Tainer, John A.; Liddington, Robert C.; Smith, Jeffrey W.

2013-01-01

SUMMARY The M16 family of zinc peptidases comprises a pair of homologous domains that form two halves of a ‘‘clam-shell’’ surrounding the active site. The M16A and M16C subfamilies form one class (‘‘peptidasomes’’): they degrade 30–70 residue peptides, and adopt both open and closed conformations. The eukaryotic M16B subfamily forms a second class (‘‘processing proteases’’): they adopt a single partly-open conformation that enables them to cleave signal sequences from larger proteins. Here, we report the solution and crystal structures of a prokaryotic M16B peptidase, and demonstrate that it has features of both classes: thus, it forms stable ‘‘open’’ homodimers in solution that resemble the processing proteases; but the clam-shell closes upon binding substrate, a feature of the M16A/C peptidasomes. Moreover, clam-shell closure is required for proteolytic activity. We predict that other prokaryotic M16B family members will form dimeric peptidasomes, and propose a model for the evolution of the M16 family. PMID:19913481

Functionalization of multi-walled carbon nanotubes by epoxide ring-opening polymerization

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

Jin Fanlong; Rhee, Kyong Yop; Park, Soo-Jin, E-mail: sjpark@inha.ac.kr

2011-12-15

In this study, covalent functionalization of carbon nanotubes (CNTs) was accomplished by surface-initiated epoxide ring-opening polymerization. FT-IR spectra showed that polyether and epoxide group covalently attached to the sidewalls of CNTs. TGA results indicated that the polyether was successfully grown from the CNT surface, with the final products having a polymer weight percentage of ca. 14-74 wt%. The O/C ratio of CNTs increased significantly from 5.1% to 29.8% after surface functionalization of CNTs. SEM and TEM images of functionalized CNTs exhibited that the tubes were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs atmore » the center. - Graphical abstract: Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers, forming core-shell structures with CNTs at the center. Highlights: Black-Right-Pointing-Pointer CNTs were functionalized by epoxide ring-opening polymerization. Black-Right-Pointing-Pointer Polyether and epoxide group covalently attached to the sidewalls of CNTs. Black-Right-Pointing-Pointer Functionalized CNTs have a polymer weight percentage of ca. 14-74 wt%. Black-Right-Pointing-Pointer Functionalized CNTs were enwrapped by polymer chains with thickness of several nanometers.« less

Synthesis of Core-Shell Nanoparticle Composites

DTIC Science & Technology

2010-08-17

Mawson Institute, University of South Australia 1 Final Report Contract Number FA2386-09-1-4043 Synthesis of Core-Shell Nanoparticle Composites...CI: Peter Majewski, School of Advanced Manufacturing and Mechanical Engineering, Mawson Institute, University of South Australia, peter.majewski...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) University of South Australia, Mawson Lakes Blvd., Mawson Lakes SA, Australia

Shell Extracts from the Marine Bivalve Pecten maximus Regulate the Synthesis of Extracellular Matrix in Primary Cultured Human Skin Fibroblasts

PubMed Central

Latire, Thomas; Legendre, Florence; Bigot, Nicolas; Carduner, Ludovic; Kellouche, Sabrina; Bouyoucef, Mouloud; Carreiras, Franck; Marin, Frédéric; Lebel, Jean-Marc; Galéra, Philippe; Serpentini, Antoine

2014-01-01

Mollusc shells are composed of more than 95% calcium carbonate and less than 5% of an organic matrix consisting mostly of proteins, glycoproteins and polysaccharides. Previous studies have elucidated the biological activities of the shell matrices from bivalve molluscs on skin, especially on the expression of the extracellular matrix components of fibroblasts. In this work, we have investigated the potential biological activities of shell matrix components extracted from the shell of the scallop Pecten maximus on human fibroblasts in primary culture. Firstly, we demonstrated that shell matrix components had different effects on general cellular activities. Secondly, we have shown that the shell matrix components stimulate the synthesis of type I and III collagens, as well as that of sulphated GAGs. The increased expression of type I collagen is likely mediated by the recruitment of transactivating factors (Sp1, Sp3 and human c-Krox) in the −112/−61 bp COL1A1 promoter region. Finally, contrarily to what was obtained in previous works, we demonstrated that the scallop shell extracts have only a small effect on cell migration during in vitro wound tests and have no effect on cell proliferation. Thus, our research emphasizes the potential use of shell matrix of Pecten maximus for dermo-cosmetic applications. PMID:24949635

Growth of InAs/InP core-shell nanowires with various pure crystal structures.

PubMed

Gorji Ghalamestani, Sepideh; Heurlin, Magnus; Wernersson, Lars-Erik; Lehmann, Sebastian; Dick, Kimberly A

2012-07-20

We have studied the epitaxial growth of an InP shell on various pure InAs core nanowire crystal structures by metal-organic vapor phase epitaxy. The InP shell is grown on wurtzite (WZ), zinc-blende (ZB), and {111}- and {110}-type faceted ZB twin-plane superlattice (TSL) structures by tuning the InP shell growth parameters and controlling the shell thickness. The growth results, particularly on the WZ nanowires, show that homogeneous InP shell growth is promoted at relatively high temperatures (∼500 °C), but that the InAs nanowires decompose under the applied conditions. In order to protect the InAs core nanowires from decomposition, a short protective InP segment is first grown axially at lower temperatures (420-460 °C), before commencing the radial growth at a higher temperature. Further studies revealed that the InP radial growth rate is significantly higher on the ZB and TSL nanowires compared to WZ counterparts, and shows a strong anisotropy in polar directions. As a result, thin shells were obtained during low temperature InP growth on ZB structures, while a higher temperature was used to obtain uniform thick shells. In addition, a schematic growth model is suggested to explain the basic processes occurring during the shell growth on the TSL crystal structures.

Gastropod shell size and architecture influence the applicability of methods used to estimate internal volume.

PubMed

Ragagnin, Marilia Nagata; Gorman, Daniel; McCarthy, Ian Donald; Sant'Anna, Bruno Sampaio; de Castro, Cláudio Campi; Turra, Alexander

2018-01-11

Obtaining accurate and reproducible estimates of internal shell volume is a vital requirement for studies into the ecology of a range of shell-occupying organisms, including hermit crabs. Shell internal volume is usually estimated by filling the shell cavity with water or sand, however, there has been no systematic assessment of the reliability of these methods and moreover no comparison with modern alternatives, e.g., computed tomography (CT). This study undertakes the first assessment of the measurement reproducibility of three contrasting approaches across a spectrum of shell architectures and sizes. While our results suggested a certain level of variability inherent for all methods, we conclude that a single measure using sand/water is likely to be sufficient for the majority of studies. However, care must be taken as precision may decline with increasing shell size and structural complexity. CT provided less variation between repeat measures but volume estimates were consistently lower compared to sand/water and will need methodological improvements before it can be used as an alternative. CT indicated volume may be also underestimated using sand/water due to the presence of air spaces visible in filled shells scanned by CT. Lastly, we encourage authors to clearly describe how volume estimates were obtained.

Proteomic analysis of the organic matrix of the abalone Haliotis asinina calcified shell

PubMed Central

2010-01-01

Background The formation of the molluscan shell is regulated to a large extent by a matrix of extracellular macromolecules that are secreted by the shell forming tissue, the mantle. This so called "calcifying matrix" is a complex mixture of proteins and glycoproteins that is assembled and occluded within the mineral phase during the calcification process. While the importance of the calcifying matrix to shell formation has long been appreciated, most of its protein components remain uncharacterised. Results Recent expressed sequence tag (EST) investigations of the mantle tissue from the tropical abalone (Haliotis asinina) provide an opportunity to further characterise the proteins in the shell by a proteomic approach. In this study, we have identified a total of 14 proteins from distinct calcified layers of the shell. Only two of these proteins have been previously characterised from abalone shells. Among the novel proteins are several glutamine- and methionine-rich motifs and hydrophobic glycine-, alanine- and acidic aspartate-rich domains. In addition, two of the new proteins contained Kunitz-like and WAP (whey acidic protein) protease inhibitor domains. Conclusion This is one of the first comprehensive proteomic study of a molluscan shell, and should provide a platform for further characterization of matrix protein functions and interactions. PMID:21050442

Biomineral shell formation under ocean acidification: a shift from order to chaos.

PubMed

Fitzer, Susan C; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S; Kamenos, Nicholas A; Phoenix, Vernon R; Cusack, Maggie

2016-02-15

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.

Biomineral shell formation under ocean acidification: a shift from order to chaos

PubMed Central

Fitzer, Susan C.; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Kamenos, Nicholas A.; Phoenix, Vernon R.; Cusack, Maggie

2016-01-01

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments. PMID:26876022

Biomineral shell formation under ocean acidification: a shift from order to chaos

NASA Astrophysics Data System (ADS)

Fitzer, Susan C.; Chung, Peter; Maccherozzi, Francesco; Dhesi, Sarnjeet S.; Kamenos, Nicholas A.; Phoenix, Vernon R.; Cusack, Maggie

2016-02-01

Biomineral production in marine organisms employs transient phases of amorphous calcium carbonate (ACC) in the construction of crystalline shells. Increasing seawater pCO2 leads to ocean acidification (OA) with a reduction in oceanic carbonate concentration which could have a negative impact on shell formation and therefore survival. We demonstrate significant changes in the hydrated and dehydrated forms of ACC in the aragonite and calcite layers of Mytilus edulis shells cultured under acidification conditions (1000 μatm pCO2) compared to present day conditions (380 μatm pCO2). In OA conditions, Mytilus edulis has more ACC at crystalisation sites. Here, we use the high-spatial resolution of synchrotron X-ray Photo Emission Electron Microscopy (XPEEM) combined with X-ray Absorption Spectroscopy (XAS) to investigate the influence of OA on the ACC formation in the shells of adult Mytilus edulis. Electron Backscatter Diffraction (EBSD) confirms that OA reduces crystallographic control of shell formation. The results demonstrate that OA induces more ACC formation and less crystallographic control in mussels suggesting that ACC is used as a repair mechanism to combat shell damage under OA. However, the resultant reduced crystallographic control in mussels raises concerns for shell protective function under predation and changing environments.

38. Historic American Buildings Survey E. W. Russell, Photographer, May ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

38. Historic American Buildings Survey E. W. Russell, Photographer, May 7, 1936 N. W. SIDE OF ROTUNDA, 3rd FLOOR, SHOWING W. AND N. HALLS AND STAIR OPENING - Spring Hill College, Main Building, Old Shell Road, Spring Hill, Mobile County, AL

Comparative analysis of early ontogeny in Bursatella leachii and Aplysia californica

PubMed Central

Vue, Zer; Capo, Thomas R.; Bardales, Ana T.

2014-01-01

Opisthobranch molluscs exhibit fascinating body plans associated with the evolution of shell loss in multiple lineages. Sea hares in particular are interesting because Aplysia californica is a well-studied model organism that offers a large suite of genetic tools. Bursatella leachii is a related tropical sea hare that lacks a shell as an adult and therefore lends itself to comparative analysis with A. californica. We have established an enhanced culturing procedure for B. leachii in husbandry that enabled the study of shell formation and loss in this lineage with respect to A. californica life staging. PMID:25538871

Oyster Shell Recycling and Bone Waste Treatment Using Plasma Pyrolysis

NASA Astrophysics Data System (ADS)

Jae, Ou Chae; Knak, S. P.; Knak, A. N.; Koo, H. J.; Ravi, V.

2006-11-01

Investigations on the recycling of oyster shells and bone waste treatment using the plasma pyrolysis technique are presented in this paper. A arc based plasma torch operated at 25 kW was employed for the experiments. Fresh oyster shells were recycled using the plasma torch to convert them to a useful product such as CaO. Bone waste was treated to remove the infectious organic part and to vitrify the inorganic part. The time required for treatment in both cases was significantly short. Significant reduction in the weight of the samples was observed in both cases.

Superlattices assembled through shape-induced directional binding

NASA Astrophysics Data System (ADS)

Lu, Fang; Yager, Kevin G.; Zhang, Yugang; Xin, Huolin; Gang, Oleg

2015-04-01

Organization of spherical particles into lattices is typically driven by packing considerations. Although the addition of directional binding can significantly broaden structural diversity, nanoscale implementation remains challenging. Here we investigate the assembly of clusters and lattices in which anisotropic polyhedral blocks coordinate isotropic spherical nanoparticles via shape-induced directional interactions facilitated by DNA recognition. We show that these polyhedral blocks--cubes and octahedrons--when mixed with spheres, promote the assembly of clusters with architecture determined by polyhedron symmetry. Moreover, three-dimensional binary superlattices are formed when DNA shells accommodate the shape disparity between nanoparticle interfaces. The crystallographic symmetry of assembled lattices is determined by the spatial symmetry of the block's facets, while structural order depends on DNA-tuned interactions and particle size ratio. The presented lattice assembly strategy, exploiting shape for defining the global structure and DNA-mediation locally, opens novel possibilities for by-design fabrication of binary lattices.

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

Lu, Fang; Yager, Kevin G.; Zhang, Yugang

Organization of spherical particles into lattices is typically driven by packing considerations. Although the addition of directional binding can significantly broaden structural diversity, nanoscale implementation remains challenging. Here we investigate the assembly of clusters and lattices in which anisotropic polyhedral blocks coordinate isotropic spherical nanoparticles via shape-induced directional interactions facilitated by DNA recognition. We show that these polyhedral blocks—cubes and octahedrons—when mixed with spheres, promote the assembly of clusters with architecture determined by polyhedron symmetry. Moreover, three-dimensional binary superlattices are formed when DNA shells accommodate the shape disparity between nanoparticle interfaces. The crystallographic symmetry of assembled lattices is determined bymore » the spatial symmetry of the block’s facets, while structural order depends on DNA-tuned interactions and particle size ratio. Lastly, the presented lattice assembly strategy, exploiting shape for defining the global structure and DNA-mediation locally, opens novel possibilities for by-design fabrication of binary lattices.« less

Methyl-modified silica nanobowl for 2D self-organized nanostructure with hydrophobic performance.

PubMed

Chen, Lingling; Sun, Aihua; Wang, Biao; Xu, Gaojie

2018-07-20

A facial method of fabricating methyl-modified silica nanobowl using a polystyrene template with tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) as co-precursors was reported. The morphology of the nanobowl was determined by the mole ratio of TEOS and MTES, and the size and shell thickness of the PS@SiO 2 . And the 2D ordered nanostructure has also been developed with a nanobowl opening perpendicular to the glass substrate surface by the Langmuir-Blodgett technique. These 2D ordered nanobowl structures present an adjustable antireflection property. The single-side nanobowl coating has a transmission improvement of 4.5% compared to the uncoated glass at a wavelength of 540 nm. Furthermore, the nanobowl structures have good hydrophobicity with a contact angle up to 130° without any additional treatment. The quantitative deformation behavior of the methyl-modified silica nanobowl was also discussed.

Superlattices assembled through shape-induced directional binding

DOE PAGES

Lu, Fang; Yager, Kevin G.; Zhang, Yugang; ...

2015-04-23

Organization of spherical particles into lattices is typically driven by packing considerations. Although the addition of directional binding can significantly broaden structural diversity, nanoscale implementation remains challenging. Here we investigate the assembly of clusters and lattices in which anisotropic polyhedral blocks coordinate isotropic spherical nanoparticles via shape-induced directional interactions facilitated by DNA recognition. We show that these polyhedral blocks—cubes and octahedrons—when mixed with spheres, promote the assembly of clusters with architecture determined by polyhedron symmetry. Moreover, three-dimensional binary superlattices are formed when DNA shells accommodate the shape disparity between nanoparticle interfaces. The crystallographic symmetry of assembled lattices is determined bymore » the spatial symmetry of the block’s facets, while structural order depends on DNA-tuned interactions and particle size ratio. Lastly, the presented lattice assembly strategy, exploiting shape for defining the global structure and DNA-mediation locally, opens novel possibilities for by-design fabrication of binary lattices.« less

Thickness constraints on the icy shells of the galilean satellites from a comparison of crater shapes.

PubMed

Schenk, Paul M

2002-05-23

A thin outer ice shell on Jupiter's large moon Europa would imply easy exchange between the surface and any organic or biotic material in its putative subsurface ocean. The thickness of the outer ice shell is poorly constrained, however, with model-dependent estimates ranging from a few kilometres to ten or more kilometres. Here I present measurements of depths of impact craters on Europa, Ganymede and Callisto that reveal two anomalous transitions in crater shape with diameter. The first transition is probably related to temperature-dependent ductility of the crust at shallow depths (7 8 km on Europa). The second transition is attributed to the influence of subsurface oceans on all three satellites, which constrains Europa's icy shell to be at least 19 km thick. The icy lithospheres of Ganymede and Callisto are equally ice-rich, but Europa's icy shell has a thermal structure about 0.25 0.5 times the thicknesses of Ganymede's or Callisto's shells, depending on epoch. The appearances of the craters on Europa are inconsistent with thin-ice-shell models and indicate that exchange of oceanic and surface material could be difficult.

Influence of SiO2 shell thickness on power conversion efficiency in plasmonic polymer solar cells with Au nanorod@SiO2 core-shell structures

PubMed Central

Zhang, Ran; Zhou, Yongfang; Peng, Ling; Li, Xue; Chen, Shufen; Feng, Xiaomiao; Guan, Yuqiao; Huang, Wei

2016-01-01

Locating core-shell metal nanoparticles into a photoactive layer or at the interface of photoactive layer/hole extraction layer is beneficial for fully employing surface plasmon energy, thus enhancing power conversion efficiency (PCE) in plasmonic organic photovoltaic devices (OPVs). Herein, we first investigated the influence of silica shell thickness in Au nanorods (NRs)@SiO2 core-shell structures on OPV performances by inserting them into poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and thieno[3,4-b]thiophene/benzodithiophene (PTB7) interface, and amazedly found that a 2–3 nm silica shell onto Au NRs induces a highest short-circuit current density of 21.2 mA cm−2 and PCE of 9.55%. This is primarily due to an extremely strong local field and a much slower attenuation of localized surface plasmon resonance around ultrathin silica-coated Au NRs, with which the field intensity remains a high value in the active layer, thus sufficiently improves the absorption of PTB7. Our work provides a clear design concept on precise control of the shell of metal nanoparticles to realize high performances in plasmonic OPVs. PMID:27125309

Influence of SiO2 shell thickness on power conversion efficiency in plasmonic polymer solar cells with Au nanorod@SiO2 core-shell structures.

PubMed

Zhang, Ran; Zhou, Yongfang; Peng, Ling; Li, Xue; Chen, Shufen; Feng, Xiaomiao; Guan, Yuqiao; Huang, Wei

2016-04-29

Locating core-shell metal nanoparticles into a photoactive layer or at the interface of photoactive layer/hole extraction layer is beneficial for fully employing surface plasmon energy, thus enhancing power conversion efficiency (PCE) in plasmonic organic photovoltaic devices (OPVs). Herein, we first investigated the influence of silica shell thickness in Au nanorods (NRs)@SiO2 core-shell structures on OPV performances by inserting them into poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and thieno[3,4-b]thiophene/benzodithiophene (PTB7) interface, and amazedly found that a 2-3 nm silica shell onto Au NRs induces a highest short-circuit current density of 21.2 mA cm(-2) and PCE of 9.55%. This is primarily due to an extremely strong local field and a much slower attenuation of localized surface plasmon resonance around ultrathin silica-coated Au NRs, with which the field intensity remains a high value in the active layer, thus sufficiently improves the absorption of PTB7. Our work provides a clear design concept on precise control of the shell of metal nanoparticles to realize high performances in plasmonic OPVs.

Core-shell polymer nanoparticles for prevention of GSH drug detoxification and cisplatin delivery to breast cancer cells

NASA Astrophysics Data System (ADS)

Surnar, Bapurao; Sharma, Kavita; Jayakannan, Manickam

2015-10-01

Platinum drug delivery against the detoxification of cytoplasmic thiols is urgently required for achieving efficacy in breast cancer treatment that is over expressed by glutathione (GSH, thiol-oligopeptide). GSH-resistant polymer-cisplatin core-shell nanoparticles were custom designed based on biodegradable carboxylic functional polycaprolactone (PCL)-block-poly(ethylene glycol) diblock copolymers. The core of the nanoparticle was fixed as 100 carboxylic units and the shell part was varied using various molecular weight poly(ethylene glycol) monomethyl ethers (MW of PEGs = 100-5000 g mol-1) as initiator in the ring-opening polymerization. The complexation of cisplatin aquo species with the diblocks produced core-shell nanoparticles of 75 nm core with precise size control the particles up to 190 nm. The core-shell nanoparticles were found to be stable in saline solution and PBS and they exhibited enhanced stability with increase in the PEG shell thickness at the periphery. The hydrophobic PCL layer on the periphery of the cisplatin core behaved as a protecting layer against the cytoplasmic thiol residues (GSH and cysteine) and exhibited <5% of drug detoxification. In vitro drug-release studies revealed that the core-shell nanoparticles were ruptured upon exposure to lysosomal enzymes like esterase at the intracellular compartments. Cytotoxicity studies were performed both in normal wild-type mouse embryonic fibroblast cells (Wt-MEFs), and breast cancer (MCF-7) and cervical cancer (HeLa) cell lines. Free cisplatin and polymer drug core-shell nanoparticles showed similar cytotoxicity effects in the HeLa cells. In MCF-7 cells, the free cisplatin drug exhibited 50% cell death whereas complete cell death (100%) was accomplished by the polymer-cisplatin core-shell nanoparticles. Confocal microscopic images confirmed that the core-shell nanoparticles were taken up by the MCF-7 and HeLa cells and they were accumulated both at the cytoplasm as well at peri-nuclear environments. The present investigation lays a new foundation for the polymer-based core-shell nanoparticles approach for overcoming detoxification in platinum drugs for the treatment of GSH over-expressed breast cancer cells.Platinum drug delivery against the detoxification of cytoplasmic thiols is urgently required for achieving efficacy in breast cancer treatment that is over expressed by glutathione (GSH, thiol-oligopeptide). GSH-resistant polymer-cisplatin core-shell nanoparticles were custom designed based on biodegradable carboxylic functional polycaprolactone (PCL)-block-poly(ethylene glycol) diblock copolymers. The core of the nanoparticle was fixed as 100 carboxylic units and the shell part was varied using various molecular weight poly(ethylene glycol) monomethyl ethers (MW of PEGs = 100-5000 g mol-1) as initiator in the ring-opening polymerization. The complexation of cisplatin aquo species with the diblocks produced core-shell nanoparticles of 75 nm core with precise size control the particles up to 190 nm. The core-shell nanoparticles were found to be stable in saline solution and PBS and they exhibited enhanced stability with increase in the PEG shell thickness at the periphery. The hydrophobic PCL layer on the periphery of the cisplatin core behaved as a protecting layer against the cytoplasmic thiol residues (GSH and cysteine) and exhibited <5% of drug detoxification. In vitro drug-release studies revealed that the core-shell nanoparticles were ruptured upon exposure to lysosomal enzymes like esterase at the intracellular compartments. Cytotoxicity studies were performed both in normal wild-type mouse embryonic fibroblast cells (Wt-MEFs), and breast cancer (MCF-7) and cervical cancer (HeLa) cell lines. Free cisplatin and polymer drug core-shell nanoparticles showed similar cytotoxicity effects in the HeLa cells. In MCF-7 cells, the free cisplatin drug exhibited 50% cell death whereas complete cell death (100%) was accomplished by the polymer-cisplatin core-shell nanoparticles. Confocal microscopic images confirmed that the core-shell nanoparticles were taken up by the MCF-7 and HeLa cells and they were accumulated both at the cytoplasm as well at peri-nuclear environments. The present investigation lays a new foundation for the polymer-based core-shell nanoparticles approach for overcoming detoxification in platinum drugs for the treatment of GSH over-expressed breast cancer cells. Electronic supplementary information (ESI) available: TGA profile and DSC thermogram of all polymers, DLS data, AFM image, 1H-NMR, 13C-NMR, and MALDI spectra of all polymers and monomers. See DOI: 10.1039/c5nr04963f

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

Thermal annealing dynamics of carbon-coated LiFePO{sub 4} nanoparticles studied by in-situ analysis

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

Krumeich, Frank, E-mail: krumeich@inorg.chem.ethz.ch; Waser, Oliver; Pratsinis, Sotiris E.

The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO{sub 4}-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 LiFePO{sub 4}-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, LiFePO{sub 4} starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further tomore » T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO{sub 4} particles (diameter in the range 300–400 nm), in agreement with ex-situ experiments. - Graphical abstract: TEM images of a typical sample area recorded at room temperature and after heating in-situ heating reveal the growth of particles and the formation of empty carbon cages. - Highlights: • LiFePO{sub 4} coated by a carbon shell is produced by flame spray pyrolysis. • The amorphous LiFePO{sub 4} starts to crystallize at 400 °C as revealed by in-situ XRD. • Crystal growth was visualized by TEM heating experiments. • The formation of empty carbon cages starts at 700 °C.« less

Detection and use of HT and DT gamma rays to diagnose mix in ICF capsules

NASA Astrophysics Data System (ADS)

Schmitt, M. J.; Kim, Y. H.; Herrmann, H. W.; McEvoy, A. M.; Zylstra, A.; Leatherland, A.; Gales, S.

2015-11-01

Recent results from Omega capsule implosion experiments containing HT-rich gas mixtures indicate that the 19.8 MeV gamma ray from aneutronic HT fusion can be measured using existing time-resolved gas Cherenkov detectors (GCDs). Additional dedicated experiments to characterize HT- γ emission in ICF experiments already have been planned. The concurrent temporally-resolved measurement of both HT- γs and DT- γs opens the door for in-depth exploration of interface mix in gas-filled ICF capsules. We propose a method to temporally resolve and observe the evolution of shell material into the capsule core as a function of fuel/shell interface temperature (which can be varied by varying the capsule shell thickness). Our proposed method uses a CD-lined plastic capsule filled with 50/50 HT gas and diagnosed using GCDs to temporally resolve both the HT ``clean'' and DT ``mix'' gamma ray burn histories. It will be shown that these burn history profiles are sensitive to the depth to which shell material mixes into the gas region. An experiment to observe these differences as a function of capsule shell thickness is proposed to determine if interface mixing is consistent with thermal diffusion (λion ~Tion2 /Zion2 ρ) at the gas/shell interface. Since hydrodynamic mixing from shell perturbations, such as the mounting stalk and glue, could complicate these types of capsule-averaged temporal measurements, simulations including their effects also will be shown. This research supported by the US DOE/NNSA, performed in part at LANL, operated by LANS LLC under contract DE-AC52-06NA25396.

Buckling shells are also swimmers

NASA Astrophysics Data System (ADS)

Quilliet, Catherine; Dyfcom Bubbleboost Team

We present an experimental and numerical study on the displacement of shells undergoing deformations in a fluid. When submitted to cycles of pressure difference between outside and inside, a shell buckles and debuckles, showing a succession of shapes and a dynamics that are different during the two phases. Hence such objects are likely to swim, including at low Reynolds (microscopic scale). We studied the swimming of buckling/debuckling shells at macroscopic scale using different approaches (force quantization, shape recording, displacement along a frictionless rail, study of external flow using PIV), and showed that inertia plays a role in propulsion, even in situations where dimensionless numbers correspond also to microswimmers in water. Different fluid viscosities were explored, showing an optimum for the displacement. Interestingly, the most favorable cases lead to displacements in the same direction and sense during both motor stroke (buckling phase) and recovery stroke (de-buckling phase). This work opens the route for the synthesis with high throughput of abusively simple synthetic swimmers, possibly gathered into nanorobots, actuated by a scalar field such as the pressure in echographic devices. Universite Grenoble Alpes, CNRS, European Research Council.

Dependence of nonlinear optical properties of Ag2S@ZnS core-shells on Zinc precursor and capping agent

NASA Astrophysics Data System (ADS)

Dehghanipour, M.; Khanzadeh, M.; Karimipour, M.; Molaei, M.

2018-03-01

In this research, four different types of Ag2S@ZnS core-shells were synthesized and their nonlinear optical (NLO) properties were investigated using a Z-scan technique by a 532 nm laser diode. Here, Ag2S and ZnS nanoparticles were also synthesized and their NLO properties were compared with Ag2S@ZnS core-shells. It was observed that the NLO properties of Ag2S@ZnS quantum dots significantly increased by increasing the values of Zn(NO3)2 and thioglycolic acid (TGA). It was also observed that the NLO properties of Ag2S@ZnS core-shells for 0.1 g of Zn(NO3)2 and 7000 μl TGA is higher than sole Ag2S and ZnS nanoparticles. In open aperture Z-scan curve of ZnS sample, a saturable absorption peak was observed and this peak was seen also in type of Ag2S@ZnS nanoparticles which the value of Zn(NO3)2 much more.

Hydrazine-Assisted Formation of Indium Phosphide (InP)-Based Nanowires and Core-Shell Composites

PubMed Central

Patzke, Greta R.; Kontic, Roman; Shiolashvili, Zeinab; Makhatadze, Nino; Jishiashvili, David

2012-01-01

Indium phosphide nanowires (InP NWs) are accessible at 440 °C from a novel vapor phase deposition approach from crystalline InP sources in hydrazine atmospheres containing 3 mol % H2O. Uniform zinc blende (ZB) InP NWs with diameters around 20 nm and lengths up to several tens of micrometers are preferably deposited on Si substrates. InP particle sizes further increase with the deposition temperature. The straightforward protocol was extended on the one-step formation of new core-shell InP–Ga NWs from mixed InP/Ga source materials. Composite nanocables with diameters below 20 nm and shells of amorphous gallium oxide are obtained at low deposition temperatures around 350 °C. Furthermore, InP/Zn sources afford InP NWs with amorphous Zn/P/O-coatings at slightly higher temperatures (400 °C) from analogous setups. At 450 °C, the smooth outer layer of InP-Zn NWs is transformed into bead-shaped coatings. The novel combinations of the key semiconductor InP with isotropic insulator shell materials open up interesting application perspectives in nanoelectronics. PMID:28809296

Activated coconut shell charcoal carbon using chemical-physical activation

NASA Astrophysics Data System (ADS)

Budi, Esmar; Umiatin, Nasbey, Hadi; Bintoro, Ridho Akbar; Wulandari, Futri; Erlina

2016-02-01

The use of activated carbon from natural material such as coconut shell charcoal as metal absorbance of the wastewater is a new trend. The activation of coconut shell charcoal carbon by using chemical-physical activation has been investigated. Coconut shell was pyrolized in kiln at temperature about 75 - 150 °C for about 6 hours in producing charcoal. The charcoal as the sample was shieved into milimeter sized granule particle and chemically activated by immersing in various concentration of HCl, H3PO4, KOH and NaOH solutions. The samples then was physically activated using horizontal furnace at 400°C for 1 hours in argon gas environment with flow rate of 200 kg/m3. The surface morphology and carbon content of activated carbon were characterized by using SEM/EDS. The result shows that the pores of activated carbon are openned wider as the chemical activator concentration is increased due to an excessive chemical attack. However, the pores tend to be closed as further increasing in chemical activator concentration due to carbon collapsing.

Hydrazine-Assisted Formation of Indium Phosphide (InP)-Based Nanowires and Core-Shell Composites.

PubMed

Patzke, Greta R; Kontic, Roman; Shiolashvili, Zeinab; Makhatadze, Nino; Jishiashvili, David

2012-12-27

Indium phosphide nanowires (InP NWs) are accessible at 440 °C from a novel vapor phase deposition approach from crystalline InP sources in hydrazine atmospheres containing 3 mol % H₂O. Uniform zinc blende (ZB) InP NWs with diameters around 20 nm and lengths up to several tens of micrometers are preferably deposited on Si substrates. InP particle sizes further increase with the deposition temperature. The straightforward protocol was extended on the one-step formation of new core-shell InP-Ga NWs from mixed InP/Ga source materials. Composite nanocables with diameters below 20 nm and shells of amorphous gallium oxide are obtained at low deposition temperatures around 350 °C. Furthermore, InP/Zn sources afford InP NWs with amorphous Zn/P/O-coatings at slightly higher temperatures (400 °C) from analogous setups. At 450 °C, the smooth outer layer of InP-Zn NWs is transformed into bead-shaped coatings. The novel combinations of the key semiconductor InP with isotropic insulator shell materials open up interesting application perspectives in nanoelectronics.

A 120-year record of resilience to environmental change in brachiopods.

PubMed

Cross, Emma L; Harper, Elizabeth M; Peck, Lloyd S

2018-06-01

The inability of organisms to cope in changing environments poses a major threat to their survival. Rising carbon dioxide concentrations, recently exceeding 400 μatm, are rapidly warming and acidifying our oceans. Current understanding of organism responses to this environmental phenomenon is based mainly on relatively short- to medium-term laboratory and field experiments, which cannot evaluate the potential for long-term acclimation and adaptation, the processes identified as most important to confer resistance. Here, we present data from a novel approach that assesses responses over a centennial timescale showing remarkable resilience to change in a species predicted to be vulnerable. Utilising museum collections allows the assessment of how organisms have coped with past environmental change. It also provides a historical reference for future climate change responses. We evaluated a unique specimen collection of a single species of brachiopod (Calloria inconspicua) collected every decade from 1900 to 2014 from one sampling site. The majority of brachiopod shell characteristics remained unchanged over the past century. One response, however, appears to reinforce their shell by constructing narrower punctae (shell perforations) and laying down more shell. This study indicates one of the most calcium-carbonate-dependent species globally to be highly resilient to environmental change over the last 120 years and provides a new insight for how similar species might react and possibly adapt to future change. © 2018 The Authors. Global Change Biology Published by John Wiley & Sons Ltd.

From middens to modern estuaries, oyster shells sequester source-specific nitrogen

NASA Astrophysics Data System (ADS)

Darrow, Elizabeth S.; Carmichael, Ruth H.; Andrus, C. Fred T.; Jackson, H. Edwin

2017-04-01

Oysters (Crassostrea virginica) were an important food resource for native peoples of the northern Gulf of Mexico, who deposited waste shells in middens. Nitrogen (N) stable isotopes (δ15N) in bivalve shells have been used as modern proxies for estuarine N sources because they approximate δ15N in suspended particulate matter. We tested the use of midden shell δ15N as a proxy for ancient estuarine N sources. We hypothesized that isotopic signatures in ancient shells from coastal Mississippi would differ from modern shells due to increased anthropogenic N sources, such as wastewater, through time. We decalcified shells using an acidification technique previously developed for modern bivalves, but modified to determine δ15N, δ13C, %N, and % organic C of these low-N, high-C specimens. The modified method resulted in the greatest percentage of usable data from midden shells. Our results showed that oyster shell δ15N did not significantly differ between ancient (500-2100 years old) and modern oysters from the same locations where the sites had undergone relatively little land-use change. δ15N values in modern shells, however, were positively correlated with water column nitrate concentrations associated with urbanization. When N content and total shell mass were combined, we estimated that middens sequestered 410-39,000 kg of relic N, buried at a rate of up to 5 kg N m-2 yr-1. This study provides a relatively simple technique to assess baseline conditions in ecosystems over long time scales by demonstrating that midden shells can be an indicator of pre-historic N source to estuaries and are a potentially significant but previously uncharacterized estuarine N sink.

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.

Exploring the novel donor-nanotube archetype as an efficient third-order nonlinear optical material: asymmetric open-shell carbon nanotubes.

PubMed

Muhammad, Shabbir; Nakano, Masayoshi; Al-Sehemi, Abdullah G; Irfan, Ahmad; Chaudhry, Aijaz Rasool; Tonami, Takayoshi; Ito, Soichi; Kishi, Ryohei; Kitagawa, Yasutaka

2018-06-06

Contrary to the enormous number of previous studies on carbon nanotubes (CNTs), herein, we realized the origin of the intrinsic open-shell diradical character and second hyperpolarizability γ using a broken symmetry approach. This study was inspired by our recent findings (S. Muhammad, et al., Nanoscale, 2016, 8, 17998 and Nakano, et al., J. Phys. Chem. C, 2016, 120, 1193). We performed structural modifications through a unique asymmetric donor-nanotube framework, which led to a novel paradigm of modified CNTs with tunable open-shell diradical character and remarkably superior NLO response properties. Interestingly, asymmetry and diradical character were found to be the crucial factors to modulate the second hyperpolarizability γ. We initially performed a comparative analysis of the diradical characters and γ amplitudes of boron nitride nanotubes (BNNTs) and CNTs possessing significant ionic characters and covalent characters, respectively. The basic findings for these simple configurations were further extended to the donor-acceptor CNT paradigm, which finally led to excellent asymmetric donor-CNT configurations with remarkably larger γ amplitudes. Furthermore, among the CNTs, finite length zigzag CNT(6,0)3 were modified with different donor-acceptor configurations. Interestingly, for the first time, unique donor-nanotube configurations [1,4-(NH2)2CNT-(6,0)3 and 1,4-(NH2)2CNT-(6,0)5] were found; they showed significantly robust γ amplitudes as large as 2519 × 103 and 4090 × 103 a.u. at the LC-UBLYP(μ = 0.33)/6-31G* level of theory. Additionally, several molecular level insights have been obtained for these novel donor-nanotube configurations using their odd electron densities, molecular electrostatic maps, densities of states and γ density analyses to highlight the realization of these novel materials for highly efficient optical and NLO applications.

Effective Role of Magnetic Core-Shell Nanocomposites in Removing Organic and Inorganic Wastes from Water.

PubMed

Shah, Nasrullah; Claessyns, Frederick; Rimmer, Stephen; Arain, Muhammad Balal; Rehan, Touseef; Wazwaz, Aref; Ahmad, Mohammad Wasi; Ul-Islam, Mazhar

2016-01-01

Affordable and efficient water treatment process to produce water free from various contaminants is a big challenge. The presence of toxic heavy metals, dyes, hazardous chemicals and other toxins causes contamination of water sources and our food chain and make them hazardous to living organisms. The current water treatment processes are no longer sustainable due to high cost and low efficiency. Due to advantageous properties, nanotechnology based materials can play a great role in increasing the efficiency of water treatment processes. Magnetic nanocomposites use nano as well as magnetic properties and have the potential to provide a sophisticated system to overcome most of the impurities present in water. There is a diversity of magnetic nanocomposites, however presently we have focussed the core-shell magnetic nanocomposites because they have excellent magnetic and separation properties, stability, and good biocompatibility. We collected systematically the bibliographic data bases for peer-reviewed research literature focusing on the theme of our review. The quality of the included research papers are selected by standard tools. A conceptual frame work is designed to arrange the topics and extracted the interventions and findings of the included studies. The overall study was divided into sections and each section incorporated the most appropriate literature citation. Total one hundred and eight references were included of which 32 references were used for basic description/introduction of core-shell magnetic nanocomposites. One review paper containing the synthesis methods for core shell magnetic nanocomposites is included while majority (76) of the references are included for comprehensive description of applications of the core-shell nanocomposites among which 25 were for dyes removal, 27 for hazardous metals, 07 for hazardous chemicals, 12 for pesticides and biological contaminants removal and five other including patents were added as miscellaneous substances removal from water sources. This review identified the effective role of core-shell magnetic nanocomposites for environmental remediation in terms of removal of various hazardous substances from water resources. The outcome of the present review confirms that the magnetic core-shell nanocomposites provide a cost effective and efficient way for the removal of various toxic substances including dyes, heavy metals, toxic organic chemicals, pesticides and some biological contaminants from water sources.

Complexation Enhancement Drives Water-to-Oil Ion Transport: A Simulation Study

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

Qiao, Baofu; Ferru, Geoffroy; Ellis, Ross J.

We address the structures and energetics of ion solvation in aqueous and organic solutions to understand liquid-liquid ion transport. Atomistic molecular dynamics (MD) simulations with polarizable force field are performed to study the coordination transformations driving lanthanide (Ln(III)) and nitrate ion transport between aqueous and an alkylamide-oil solution. An enhancement of the coordination behavior in the organic phase is achieved in contrast with the aqueous solution. In particular, the coordination number of Ce3+ increases from 8.9 in the aqueous to 9.9 in the organic solutions (from 8 in the aqueous to 8.8 in the organic systems for Yb3+). Moreover, themore » local coordination environ ment changes dramatically. Potential of mean force calculations show that the Ln(III)-ligand coordination interaction strengths follow the order of Ln(III-)nitrate> Ln(III)-water>Ln(III)-DMDBTDMA. They increase 2-fold in the lipophilic environment in comparison to the aqueous phase, and we attribute this to the shedding of the outer solvation shell. Our findings highlight the importance of outer sphere interactions on the competitive solvation energetics that cause ions to migrate between immiscible phases; an essential ingredient for advancing important applications such as rare earth metal separations. Some open questions in simulating the coordination behavior of heavy metals are also addressed.« less

Discussion on Microwave-Matter Interaction Mechanisms by In Situ Observation of "Core-Shell" Microstructure during Microwave Sintering.

PubMed

Liu, Wenchao; Xu, Feng; Li, Yongcun; Hu, Xiaofang; Dong, Bo; Xiao, Yu

2016-02-23

This research aims to deepen the understanding of the interaction mechanisms between microwave and matter in a metal-ceramic system based on in situ synchrotron radiation computed tomography. A special internal "core-shell" microstructure was discovered for the first time and used as an indicator for the interaction mechanisms between microwave and matter. Firstly, it was proved that the microwave magnetic field acted on metal particles by way of inducing an eddy current in the surface of the metal particles, which led to the formation of a "core-shell" microstructure in the metal particles. On this basis, it was proposed that the ceramic particles could change the microwave field and open a way for the microwave, thereby leading to selective heating in the region around the ceramic particles, which was verified by the fact that all the "core-shell" microstructure was located around ceramic particles. Furthermore, it was indicated that the ceramic particles would gather the microwaves, and might lead to local heating in the metal-ceramic contact region. The focusing of the microwave was proved by the quantitative analysis of the evolution rate of the "core-shell" microstructure in a different region. This study will help to reveal the microwave-matter interaction mechanisms during microwave sintering.

Triggered high-purity telecom-wavelength single-photon generation from p-shell-driven InGaAs/GaAs quantum dot.

PubMed

Dusanowski, Ł; Holewa, P; Maryński, A; Musiał, A; Heuser, T; Srocka, N; Quandt, D; Strittmatter, A; Rodt, S; Misiewicz, J; Reitzenstein, S; Sęk, G

2017-12-11

We report on the experimental demonstration of triggered single-photon emission at the telecom O-band from In(Ga)As/GaAs quantum dots (QDs) grown by metal-organic vapor-phase epitaxy. Micro-photoluminescence excitation experiments allowed us to identify the p-shell excitonic states in agreement with high excitation photoluminescence on the ensemble of QDs. Hereby we drive an O-band-emitting GaAs-based QD into the p-shell states to get a triggered single photon source of high purity. Applying pulsed p-shell resonant excitation results in strong suppression of multiphoton events evidenced by the as measured value of the second-order correlation function at zero delay of 0.03 (and ~0.005 after background correction).

Formation of Double-Shelled Zinc-Cobalt Sulfide Dodecahedral Cages from Bimetallic Zeolitic Imidazolate Frameworks for Hybrid Supercapacitors.

PubMed

Zhang, Peng; Guan, Bu Yuan; Yu, Le; Lou, Xiong Wen David

2017-06-12

Complex metal-organic frameworks used as precursors allow design and construction of various nanostructured functional materials which might not be accessible by other methods. Here, we develop a sequential chemical etching and sulfurization strategy to prepare well-defined double-shelled zinc-cobalt sulfide (Zn-Co-S) rhombic dodecahedral cages (RDCs). Yolk-shelled zinc/cobalt-based zeolitic imidazolate framework (Zn/Co-ZIF) RDCs are first synthesized by a controlled chemical etching process, followed by a hydrothermal sulfurization reaction to prepare double-shelled Zn-Co-S RDCs. Moreover, the strategy reported in this work enables easy control of the Zn/Co molar ratio in the obtained double-shelled Zn-Co-S RDCs. Owing to the structural and compositional benefits, the obtained double-shelled Zn-Co-S RDCs exhibit enhanced performance with high specific capacitance (1266 F g -1 at 1 A g -1 ), good rate capability and long-term cycling stability (91 % retention over 10,000 cycles) as a battery-type electrode material for hybrid supercapacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient photocatalytic degradation of malachite green dye under visible irradiation by water soluble ZnS:Mn/ZnS core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Khaparde, Rohini A.; Acharya, Smita A.

2018-05-01

ZnS:Mn/ ZnS core/shell nanoparticles was prepared by two step synthesis method. In first step, oleic acid - coated Mn doped ZnS core nanoparticles were prepared which were charged through ligand exchange. Shell of ZnS NPs was finally deposited upon the surface of charged Mn doped ZnS core. Scanning electron microscopy (SEM) image exhibit morphological confirmation of ZnS:Mn/ZnS core/shell. As Nano ZnS are the most suitable candidates for photocatalyst that extensively involved in degradation and complete mineralization of various toxic organic pollutants owing to its high efficiency, strong oxidizing power, non-toxicity, high photochemical and biological stability, corrosive resistance and low cost. Photodegradation of malachite green is systematically investigated by adding different molar proportional of ZnS:Mn/ZnS core/shell in the dye. The rate of de-coloration of dye is detected by UV-VIS absorption spectroscopy. Efficient detoriation in the colour of dye is attributed to the core /shell morphology of the particles.

Carbonate biomineralization in terrestrial gastropods: environmental vs. physiological constraints

NASA Astrophysics Data System (ADS)

Mierzwa, D.; Stolarski, J.

2009-04-01

Preservational potential of shells of terrestrial gastropods allows to use them as valuable (paleo)climatic proxies. Despite of the fact, that the elements incorporated in their skeleton derive almost entirely from their diet, details of the ion uptake routes have not been studied in details. This work is a first step in the investigations of element uptake and biomineralization processes in pulmonate gastropod Cepaea vindobonensis (Férussac, 1821). Although phenotypic plasticity in the shell characters of the species appears to be mainly genetic in nature, some differences seem to correlate with availability of ions used in biomineralization. For example, shells of individuals living in marginal parts of flood plains (environment extreme for the species and generally depleted in calcium) have weakened structure and faded color pattern, whereas individuals from the lime substrata form typically developed, pigmented shells with several cross-lamellar layers. Micro- and nanostructural characteristics of shells from different environments are visualized by SEM and AFM imaging techniques and some biogeochemical properties are characterized by spectroscopic and fluorescence methods. Further experiments are required to elucidate the ion/trace elements transfer between the substratum, nutrients, organism, and the shell.

Niche construction drives social dependence in hermit crabs.

PubMed

Laidre, Mark E

2012-10-23

Organisms can receive not only a genetic inheritance from their ancestors but also an ecological inheritance, involving modifications their ancestors made to the environment through niche construction. Ecological inheritances may persist as a legacy, potentially generating selection pressures that favor sociality. Yet, most proposed cases of sociality being impacted by an ecological inheritance come from organisms that live among close kin and were highly social before their niche construction began. Here, I show that in terrestrial hermit crabs (Coenobita compressus)--organisms that do not live with kin and reside alone, each in its own shell--niche-construction drives social dependence, such that individuals can only survive in remodeled shells handed down from conspecifics. These results suggest that niche construction can be an important initiator of evolutionary pressures to socialize, even among unrelated and otherwise asocial organisms. Copyright © 2012 Elsevier Ltd. All rights reserved.

KSC-07pd3037

NASA Image and Video Library

2007-10-22

KENNEDY SPACE CENTER, FLA. -- A rare photo of a Florida snapping turtle out in the open on Beach Road, near NASA's Kennedy Space Center. Found only in Florida and Georgia, this species is related to the common snapping turtle. It is considered a dangerous turtle because it can snap very quickly with its extremely strong jaws. Its tail, which is almost as long as its shell, has saw-edges along the top. The shell also has rough points down the middle. The shell is tan to dark brown and may have green algae growing on it. It can grow to 17 inches long and weigh 45 pounds. Snapping turtles usually live in ponds under the shadows and don’t like to rest in the sun like most turtles. They eat almost anything: water bugs, fish, lizards, small birds, mice, plants and even dead animals. Photo credit: NASA/Kenny Allen

KSC-07pd3035

NASA Image and Video Library

2007-10-22

KENNEDY SPACE CENTER, FLA. -- A rare photo of a Florida snapping turtle out in the open on Beach Road, near NASA's Kennedy Space Center. Found only in Florida and Georgia, this species is related to the common snapping turtle. It is considered a dangerous turtle because it can snap very quickly with its extremely strong jaws. Its tail, which is almost as long as its shell, has saw-edges along the top. The shell also has rough points down the middle. The shell is tan to dark brown and may have green algae growing on it. It can grow to 17 inches long and weigh 45 pounds. Snapping turtles usually live in ponds under the shadows and don’t like to rest in the sun like most turtles. They eat almost anything: water bugs, fish, lizards, small birds, mice, plants and even dead animals. Photo credit: NASA/Kenny Allen

KSC-07pd3036

NASA Image and Video Library

2007-10-22

KENNEDY SPACE CENTER, FLA. -- A rare photo of a Florida snapping turtle out in the open on Beach Road, near NASA's Kennedy Space Center. Found only in Florida and Georgia, this species is related to the common snapping turtle. It is considered a dangerous turtle because it can snap very quickly with its extremely strong jaws. Its tail, which is almost as long as its shell, has saw-edges along the top. The shell also has rough points down the middle. The shell is tan to dark brown and may have green algae growing on it. It can grow to 17 inches long and weigh 45 pounds. Snapping turtles usually live in ponds under the shadows and don’t like to rest in the sun like most turtles. They eat almost anything: water bugs, fish, lizards, small birds, mice, plants and even dead animals. Photo credit: NASA/Kenny Allen

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.

Publications - GMC 29 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 29 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis Reference Minder, Michael, and Shell Oil Company, 1985, Geochemical analysis (total organic carbon, rock ; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources, Division of

Publications - GMC 125 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 125 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Cunningham, K., and Shell Oil Company, 1989, Total organic carbon, rock-eval pyrolysis, and Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources, Division

Genesis Spacecraft Science Canister Preliminary Inspection and Cleaning

NASA Technical Reports Server (NTRS)

Hittle, J. D.; Calaway, M. J.; Allton, J. H.; Warren, J. L.; Schwartz, C. M.; Stansbery, E. K.

2006-01-01

The Genesis science canister is an aluminum cylinder (75 cm diameter and 35 cm tall) hinged at the mid-line for opening. This canister was cleaned and assembled in an ISO level 4 (Class 10) clean room at Johnson Space Center (JSC) prior to launch. The clean solar collectors were installed and the canister closed in the cleanroom to preserve collector cleanliness. The canister remained closed until opened on station at Earth-Sun L1 for solar wind collection. At the conclusion of collection, the canister was again closed to preserve collector cleanliness during Earth return and re-entry. Upon impacting the dry Utah lakebed at 300 kph the science canister integrity was breached. The canister was returned to JSC. The canister shell was briefly examined, imaged, gently cleaned of dust and packaged for storage in anticipation of future detailed examination. The condition of the science canister shell noted during this brief examination is presented here. The canister interior components were packaged and stored without imaging due to time constraints.

On the Stark effect in open shell complexes exhibiting partially quenched electronic angular momentum: Infrared laser Stark spectroscopy of OH–C 2H 2, OH–C 2H 4, and OH–H 2O

DOE PAGES

Moradi, Christopher P.; Douberly, Gary E.

2015-06-22

The Stark effect is considered for polyatomic open shell complexes that exhibit partially quenched electronic angular momentum. Matrix elements of the Stark Hamiltonian represented in a parity conserving Hund's case (a) basis are derived for the most general case, in which the permanent dipole moment has projections on all three inertial axes of the system. Transition intensities are derived, again for the most general case, in which the laser polarization has projections onto axes parallel and perpendicular to the Stark electric field, and the transition dipole moment vector is projected onto all three inertial axes in the molecular frame. Asmore » a result, simulations derived from this model are compared to experimental rovibrational Stark spectra of OH-C 2H 2, OH-C 2H 4, and OH-H 2O complexes formed in helium nanodroplets.« less

On the uniqueness of the constrained space orbital variation (CSOV) technique

NASA Technical Reports Server (NTRS)

Bauschlicher, C. W., Jr.

1986-01-01

Several CSOV analyses are performed for the 1Sigma(+) state of NiCO, and it is shown that the importance of the CO sigma donation, Ni pi back donation, and interunit polarizations are virtually independent of the order of the CSOV steps, provided that the open-shell 3d sigma and 4s Ni orbitals are orthogonalized to the CO. This order of orthogonalization is consistent with the polarization of the Ni observed in the unconstrained SCF wavefunction. If instead the CO is orthogonalized to the open-shell Ni orbitals, the frozen orbital repulsion and entire CSOV analysis becomes unphysical. A comparison of the SCF and CAS SCF descriptions for the NiCO 1Sigma(+) state shows the importance of the s to d promotion and sd hybridization in reducing the repulsion and increasing the Ni to CO pi bonding. For LiF, CSOV analyses starting from both the neutral and ionic asymptotes show the bonding to be predominantly Li(+) - F(-). These examples show the uniqueness of the CSOV decomposition.

Why Do Silver Trimers Intercalated in DNA Exhibit Unique Nonlinear Properties That Are Promising for Applications?

PubMed

Bonačić-Koutecký, Vlasta; Perić, Martina; Sanader, Željka

2018-05-17

Our investigation of one-photon absorption (OPA) and nonlinear optical (NLO) properties such as two-photon absorption (TPA) of silver trimer intercalated in DNA based on TDDFT approach allowed us to propose a mechanism responsible for large TPA cross sections of such NLO-phores. We present a concept that illustrates the key role of quantum cluster as well as of nucleotide bases from the immediate neighborhood. For this purpose, different surroundings consisting of guanine-cytosine and adenine-thymine such as (GCGC) and (ATAT) have been investigated that are exhibiting substantially different values of TPA cross sections. This has been confirmed by extending the immediate surroundings as well as using the two-layer quantum mechanics/molecular mechanics (QM/MM) approach. We focus on the cationic closed-shell system and illustrate that the neutral open-shell system shifts OPA spectra into the NIR regime, which is suitable for applications. Thus, in this contribution, we propose novel NLO-phores inducing large TPA cross sections, opening the route for multiphoton imaging.

Can magneto-plasmonic nanohybrids efficiently combine photothermia with magnetic hyperthermia?

NASA Astrophysics Data System (ADS)

Espinosa, Ana; Bugnet, Mathieu; Radtke, Guillaume; Neveu, Sophie; Botton, Gianluigi A.; Wilhelm, Claire; Abou-Hassan, Ali

2015-11-01

Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives.Multifunctional hybrid-design nanomaterials appear to be a promising route to meet the current therapeutics needs required for efficient cancer treatment. Herein, two efficient heat nano-generators were combined into a multifunctional single nanohybrid (a multi-core iron oxide nanoparticle optimized for magnetic hyperthermia, and a gold branched shell with tunable plasmonic properties in the NIR region, for photothermal therapy) which impressively enhanced heat generation, in suspension or in vivo in tumours, opening up exciting new therapeutic perspectives. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06168g

Use of nanoindentation technique for a better understanding of the fracture toughness of Strombus gigas conch shell

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

Romana, L., E-mail: laurence.romana@univ-ag.fr; Thomas, P.; Bilas, P.

2013-02-15

In this work the nanochemical properties of the composite organomineral biomaterial constituting Strombus gigas conch shell are studied by means of dynamic mechanical analyses associated to nanoidentation technique. The measurements are performed on shell samples presenting different surface orientations relative to the growth axis of the conch shell. The influence of the organic component of the biomaterial on its nanomechanical properties is also investigated by studying fresh and dried S. gigas conch shells. Monocrystalline aragonite is used as a reference. For the understanding of nanochemical behaviour, special attention is paid to the pop in events observed on the load/displacement curvesmore » which results from nanofractures' initiation and propagation occuring during the load process. In order to better understand the mechanical properties systematic studies of the structure and morphology are performed using scanning electron microscopy, atomic force microscopy and X-ray diffractometry. The hardness and Young's modulus values measured on bio aragonite samples are close to those of the aragonite mineral standard. This surprising result shows that, H and E values are not related to the bio composition and lamellar structure of the bio aragonite. However, it was found that the organic layer and the micro architecture strongly influence the nanofracture initiation and propagation processes in the samples. Statistic study of the pop-in events can help to predict the macroscopic mechanical behaviour of the material. - Highlights: ► Nanomechanical properties of Strombus gigas conch shell ► Low influence of the crossed lamellar structure on H and E values at the nano scale ► Strong influence of the crossed lamellar on nanocracks initiation ► Correlation between mechanical behaviors at the macro and nano scales.« less

Student Outlines Teaching Students to Organize Their Notes

ERIC Educational Resources Information Center

Burt, Derek

2006-01-01

Two years ago I implemented a basic outline of each class for my students to take notes on for Calculus II at the United States Military Academy. The outline provided students with a shell of the class material for each day of class. Their job was to fill in the shell as we went through the material. The outlines provided students an easy method…

Electrowetting-on-dielectrics for manipulation of oil drops and gas bubbles in aqueous-shell compound drops.

PubMed

Li, Jiang; Wang, Yixuan; Chen, Haosheng; Wan, Jiandi

2014-11-21

We present the manipulation of oil, organic and gaseous chemicals by electrowetting-on-dielectric (EWOD) technology using aqueous-shell compound drops. We demonstrate that the transport and coalescence of viscous oil drops, the reaction of bromine with styrene in benzene solution, and the reaction of red blood cells with carbon monoxide bubbles can be accomplished using this method.