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Dual latex/surfactant templating of hollow spherical silica particles with ordered mesoporous shells.

Hollow spherical silica particles with hexagonally ordered mesoporous shells are synthesized with the dual use of cetyltrimethylammonium bromide (CTAB) and unmodified polystyrene latex microspheres as templates in concentrated aqueous ammonia. In most of the hollow mesoporous particles, cylindrical pores run parallel to the hollow core due to interactions of CTAB/silica aggregates with the latices. Effects on the product structure of the CTAB:latex ratio, the amount of aqueous ammonia, and the latex size are studied. Hollow particles with hexagonally patterned mesoporous shells are obtained at moderate CTAB:latex ratios. Too little CTAB causes silica shell growth without surfactant templating, and too much induces nucleation of new mesoporous silica particles without latex cores. The concentration of ammonia must be large to induce co-assembly of CTAB, silica, and latex into dispersed particles. The results are consistent with the formation of particles by addition of CTAB/silica aggregates to the surface of latex microspheres. When the size and number density of the latex microspheres are changed, the size of the hollow core and the shell thickness can be controlled. However, if the microspheres are too small (50 nm in this case), agglomerated particles with many hollow voids are obtained, most likely due to colloidal instability.

Journal Article↗

Shell distribution on colloidal CdSe/ZnS quantum dots.

Scanning transmission electron microscopy (STEM) coupled with electron energy loss spectroscopy (EELS) was used to determine the chemical distribution of semiconductor shell material around colloidal core-shell CdSe/ZnS quantum dots (QDs). EELS signals from positions around the QD indicate a well-defined shell of ZnS surrounding the CdSe core, but the distribution of the shell material is highly anisotropic. This nonuniformity may reflect the differences in chemical activity of the crystal faces of the core QD and implies a nonoptimal QD surface passivation.

Journal Article↗

Thermal conductivity modeling of core-shell and tubular nanowires.

The heteroepitaxial growth of crystalline core-shell nanostructures of a variety of materials has become possible in recent years, allowing the realization of various novel nanoscale electronic and optoelectronic devices. The increased surface or interface area will decrease the thermal conductivity of such nanostructures and impose challenges for the thermal management of such devices. In the meantime, the decreased thermal conductivity might benefit the thermoelectric conversion efficiency. In this paper, we present modeling results on the lattice thermal conductivity of core-shell and tubular nanowires along the wire axis direction using the phonon Boltzmann equation. We report the dependence of the thermal conductivity on the surface conditions and the core-shell geometry for silicon core-germanium shell and tubular silicon nanowires at room temperature. The results show that the effective thermal conductivity changes not only with the composition of the constituents but also with the radius of the nanowires and nanopores due to the nature of the ballistic phonon transport. The results in this work have implications for the design and operation of a variety of nanoelectronic devices, optoelectronic devices, and thermoelectric materials and devices.

Electronics↗

Core-shell and segmented polymer-metal composite nanostructures.

Composite nanostructures (approximately 200 nm wide and several micrometers long) of metal and polyaniline (PANI) in two new variations of core-shell (PANI-Au) and segmented (Au-PANI and Ni-Au-PANI) architectures were fabricated electrochemically within anodized aluminum oxide (AAO) membranes. Control over the structure of these composites (including the length of the gold shells in the core-shell structures) was accomplished by adjusting the time and rate of electrodeposition and the pH of the solution from which the materials were grown. Exposure of the core-shell structures to oxygen plasma removed the PANI and yielded aligned gold nanotubes. In the segmented structures, a self-assembled monolayer (SAM) of thioaniline nucleated the growth of PANI on top of metal nanorods and acted as an adhesion layer between the metal and PANI components.

Aniline Compounds↗

The effects of electrolytic lesion to the shell subterritory of the nucleus accumbens on delayed non-matching-to-sample and four-arm baited eight-arm radial-maze tasks.

The effects of bilateral electrolytic lesions of the "shell" subterritory of the nucleus accumbens in the rat were examined on 2 tasks known to be sensitive to hippocampal damage. Experiment 1 tested the effects of shell lesion on delayed non-matching-to-sample (DNMS) task in a T-maze. The maze was rotated 180 degrees after the end of acquisition. Experiment 2 used a 4-arm baited, 4-arm unbaited, 8-arm radial-maze task and its reversal. Shell lesion led to impaired acquisition of DNMS in a T-maze and of 4-arm baited, 4-arm unbaited, 8-arm radial maze tasks, suggestive of mnemonic deficits. Following analysis of animals' choice pattern in both tasks, the deficit was interpreted as being largely due to an extensive use of response strategy. The results suggest that the inappropriate use of response strategy by shell animals was a result of their inability to switch from initial response strategy to a later, more appropriate, memory-dependent strategy.

Animals↗

Feeding induced by GABA(A) receptor stimulation within the nucleus accumbens shell: regional mapping and characterization of macronutrient and taste preference.

This study investigated the areas of the nucleus accumbens shell involved in the modulation of feeding behavior by GABAergic stimulation and characterized this response using macronutrient diets as well as saline, sucrose, and saccharin solutions. The GABA agonist muscimol induced a pronounced feeding response when infused in the medial nucleus accumbens shell but not in the ventral or lateral accumbens shell. In the macronutrient preference study, muscimol increased the intake of both high fat and high carbohydrate diets when presented separately. When both diets were available simultaneously, muscimol stimulated feeding of both diets to the same degree. Muscimol elicited a robust increase in the consumption of sucrose solution. However, no effect of muscimol was demonstrated for water, saline, or saccharin intake. These findings provide evidence for a selective role for GABA-sensitive neurons in the medial accumbens shell in the regulation of ingestive behavior and further suggest that GABA(A) receptors in this region do not modulate palatability, macronutrient selection, or rewarding properties of food.

Animals↗

Differential involvement of nucleus accumbens shell and core subregions in maternal memory in postpartum female rats.

Maternal memory refers to the long-term retention of maternal responsiveness as a consequence of animals' prior experiences with their young. This study examined the relative roles of 2 subregions of the nucleus accumbens (NA; shell and core) in maternal memory in rats. NA shell lesions either before or immediately after a short experience significantly disrupted maternal memory, but lesions after a 24-hr maternal experience had no effect. NA core lesions had no significant impact on maternal memory. Cycloheximide (a protein synthesis inhibitor) at a high dose (25 micrograms/microliter) infused in the NA shell immediately after 1 hr of maternal experience also significantly disrupted maternal memory, whereas infusions in the medial preoptic area had no effect. It was concluded that the NA shell, but not the NA core, is involved in the consolidation of maternal memory.

Animals↗

Structural basis for the fracture toughness of the shell of the conch Strombus gigas.

Natural composite materials are renowned for their mechanical strength and toughness: despite being highly mineralized, with the organic component constituting not more than a few per cent of the composite material, the fracture toughness exceeds that of single crystals of the pure mineral by two to three orders of magnitude. The judicious placement of the organic matrix, relative to the mineral phase, and the hierarchical structural architecture extending over several distinct length scales both play crucial roles in the mechanical response of natural composites to external loads. Here we use transmission electron microscopy studies and beam bending experiments to show that the resistance of the shell of the conch Strombus gigas to catastrophic fracture can be understood quantitatively by invoking two energy-dissipating mechanisms: multiple microcracking in the outer layers at low mechanical loads, and crack bridging in the shell's tougher middle layers at higher loads. Both mechanisms are intimately associated with the so-called crossed lamellar microarchitecture of the shell, which provides for 'channel' cracking in the outer layers and uncracked structural features that bridge crack surfaces, thereby significantly increasing the work of fracture, and hence the toughness, of the material. Despite a high mineral content of about 99% (by volume) of aragonite, the shell of Strombus gigas can thus be considered a 'ceramic plywood' and can guide the biomimetic design of tough, lightweight structures.

Animals↗

Omega-3 fatty acid ethyl-eicosapentaenoate attenuates IL-1beta-induced changes in dopamine and metabolites in the shell of the nucleus accumbens: involved with PLA2 activity and corticosterone secretion.

Previously, we have reported that interleukin-1 beta (IL-1) induces changes in dopaminergic (DA) and serotonergic systems in the core of the [corrected] nucleus accumbens (NAc). We have also demonstrated that n-3 fatty acid ethyl-eicosapentaenoate (EPA) can significantly reduce stress and anxiety-like behaviors, corticosterone concentrations [corrected] and peripheral inflammatory response induced by IL-1 administration. Compared to the core, the shell is involved more in emotion, stress and psychiatric diseases. However, the relationship between inflammation and the functions of DA system in the shell has not been studied. Since phospholipase (PL) A2 is a key enzyme in the [corrected] arachidonic acid-eicosanoids-prostaglandin [corrected] (PG)E2 pathway, and the change in NAc DA [corrected] system has been associated with glucocorticoid stimulation; [corrected] therefore, the hypotheses of this study are (1) that IL-1 induced changes in DA neurotransmission in the shell may be through PLA2-PGE2-corticosterone pathway; (2) EPA may attenuate IL-1 effects via inhibiting PLA2 activities, which blocks PGE2 stimulation of corticosterone. Using an in vivo microdialysis method, the present study showed that IL-1 administration significantly increased extracellular levels of DA, and its metabolites 3,4-dihydroxyphenylacetic acid, [corrected] and homovanillic acid [corrected] in the shell of the NAc. IL-1 also increased blood concentration of corticosterone and PGE2, and increased the activities of cytosolic and secretory [corrected] PLA2. IL-1-induced changes were significantly attenuated by EPA treatment. Furthermore, glucocorticoid [corrected] receptor antagonist mifepristone (RU486) pretreatment significantly blocked IL-1-induced changes in DA and metabolites. Quinacrine, [corrected] a PLA2 antagonist significantly blocked IL-1-induced [corrected] increase in PGE2 and corticosterone concentrations. These results demonstrated the hypotheses that IL-1 effects may be via PLA2-PGE2-corticosterone pathway and EPA attenuated IL-1 effects may be through the suppression of PLA2 expression, which then reduced PGE2 synthesis and corticosterone secretion.

3,4-Dihydroxyphenylacetic Acid↗

Electrochemical properties of core-shell TiC-TiO2 nanoparticle films immobilized at ITO electrode surfaces.

Titanium carbide (TiC) nanoparticles are readily deposited onto tin-doped indium oxide (ITO) electrodes in the form of thin porous films. The nanoparticle deposits are electrically highly conducting and electrochemically active. In aqueous media (at pH 7) and at applied potentials positive of 0.3 V vs. SCE partial anodic surface oxidation and formation (at least in part) of novel core-shell TiC-TiO2 nanoparticles is observed. Significant thermal oxidation of TiC nanoparticles by heating in air occurs at a temperature of 250 degrees C and leads first to core-shell TiC-TiO2 nanoparticles, next at ca. 350 degrees C to TiO2 (anatase), and finally at temperatures higher than 750 degrees C to TiO2 (rutile). Electrochemically and thermally partially oxidized TiC nanoparticles still remain very active and for some redox systems electrocatalytically active. Scanning and transmission electron microscopy (SEM and TEM), temperature dependent XRD, quartz crystal microbalance, and voltammetric measurements are reported. The electrocatalytic properties of the core-shell TiC-TiO2 nanoparticulate films are surveyed for the oxidation of hydroquinone, ascorbic acid, and dopamine in aqueous buffer media. In TiC-TiO2 core-shell nanoparticle films TiO2 surface reactivity can be combined with TiC conductivity.

Journal Article↗

Direct comparison of projections from the central amygdaloid region and nucleus accumbens shell.

Certain neurochemical and connectional characteristics common to extended amygdala and the nucleus accumbens shell suggest that the two represent a single functional-anatomical continuum. If this is so, it follows that the outputs of the two structures should be substantially similar. To address this, projections from the caudomedial shell and central nucleus of the amygdala, a key extended amygdala structure, were demonstrated in Sprague-Dawley rats with different anterograde axonal tracers processed separately to exhibit distinguishable brown and blue-black precipitates. The caudomedial shell projection is strong in the ventral pallidum and along the medial forebrain bundle through the lateral preopticohypothalamic continuum into the ventral tegmental area, distal to which it thins abruptly. The central nucleus projects strongly to the bed nucleus of the stria terminalis and the sublenticular extended amygdala, but substantially to the lateral hypothalamus only at levels behind the rostral part of the entopeduncular nucleus. Innervation of the ventral tegmental area by the central amygdala is minimal, but the lateral one-third of the substantia nigra, pars compacta and an adjacent lateral part of the retrorubral field receive substantial central amygdala input. Central amygdaloid projections are robust in caudal brainstem sites, such as the reticular formation, parabrachial nucleus, nucleus of the solitary tract and dorsal vagal complex, all of which receive little input from the accumbens. The substantial differences in the output systems of the caudomedial shell of accumbens and central amygdala suggest that the two represent distinct functional-anatomical systems.

Amygdala↗

Dopamine efflux in nucleus accumbens shell and core in response to appetitive classical conditioning.

Dopamine transmission within the nucleus accumbens has been implicated in associative reinforcement learning. We investigated the effect of appetitive classical conditioning on dopamine efflux in the rat nucleus accumbens shell and core, as dopamine may be differentially activated by conditioned and unconditioned stimuli (CS, US) in these subregions. After implantation of microdialysis cannulae, rats were food restricted and trained for three consecutive days with three acquisition sessions per day. A 10-s noise (CS) was immediately followed by the delivery of two reward pellets (US) for the conditioned group (paired presentation), whereas conditioned stimuli and unconditioned stimuli were presented at random for the control group (unpaired presentation). On the fourth day, all rats were given a further CS + US session and two CS-alone sessions, and extracellular dopamine concentrations were measured (7.5 min/per sample). Behavioural measures (number of nose pokes, latency to nose poke after conditioned stimuli onset, locomotor activity) demonstrated that the paired groups showed a high level of conditioning. CS + US presentation increased dopamine equally in both shell and core of the paired and unpaired groups. CS alone presentation induced a conditioned dopamine release only in the paired groups. No significant difference was found between shell and core. Unlike previous conditioning paradigms involving either a more salient US (foot shock, addictive drug) or a more complex CS, the present paradigm, using normal reward pellets as US and a discrete auditory stimulus as CS, did not lead to differential responses in dopamine efflux in shell and core subregions of the nucleus accumbens.

Animals↗

Opposite modulatory roles for adenosine A1 and A2A receptors on glutamate and dopamine release in the shell of the nucleus accumbens. Effects of chronic caffeine exposure.

Previous studies have demonstrated opposing roles for adenosine A1 and A2A receptors in the modulation of extracellular levels of glutamate and dopamine in the striatum. In the present study, acute systemic administration of motor-activating doses of the A2A receptor antagonist MSX-3 significantly decreased extracellular levels of dopamine and glutamate in the shell of the rat nucleus accumbens (NAc) and counteracted both dopamine and glutamate release induced by systemic administration of motor-activating doses of either the A1 receptor antagonist CPT or caffeine. Furthermore, exposure to caffeine in the drinking water (1 mg/mL, 14 days) resulted in tolerance to the effects of systemic injection of CPT or caffeine, but not MSX-3, on extracellular levels of dopamine and glutamate in the NAc shell. The present results show: first, the existence of opposite tonic effects of adenosine on extracellular levels of dopamine and glutamate in the shell of the NAc mediated by A1 and A2A receptors; second, that complete tolerance to caffeine's dopamine- and glutamate-releasing effects which develops after chronic caffeine exposure is attributable to an A1 receptor-mediated mechanism. Development of tolerance to the dopamine-releasing effects of caffeine in the shell of the NAc may explain its weak addictive properties and atypical psychostimulant profile.

Adenosine A1 Receptor Antagonists↗

Maternal blood coagulation factor XIII is associated with the development of cytotrophoblastic shell.

We analysed the early implantation tissues of normal women and of a patient with congenital factor XIII deficiency in order to study the role of maternal subunit A of factor XIII (XIIIA) in the development of extravillous cytotrophoblast. The patient had received adequate administration of factor XIIIA concentrate only up to 7 weeks of gestation (wG). Her pregnancy was maintained until the latter half of 8 wG, but was terminated by intrauterine fetal death at 9 wG. Immunohistochemical staining of cytokeratin, XIIIA and subunit S of factor XIII was performed in the early implantation tissues of normal women and of this patient. Numerous well-formed cytotrophoblastic shells and Nitabuch's layers were detected in implantation tissues at 7-8 wG in normal women, and XIIIA was present in the intercellular space in well-formed cytotrophoblastic shells, while the cytotrophoblastic shells and Nitabuch's layers in this patient's implantation tissue were poorly-formed. Furthermore, XIIIA was not detected around them. It is suggested that when the maternal plasma activity of factor XIII is low, the concentration of XIIIA at the placental bed is also low, leading to the insufficient formation of cytotrophoblastic shell and therefore an increased probability of miscarriage in patients with congenital factor XIII deficiency.

Adult↗

Two-dimensional hydration shells of alkali metal ions at a hydrophobic surface.

We study the hydration shell formation of alkali metal ions at a graphite surface. Two-dimensional shell structures are found in the initial stage of hydration, in contrast to the three-dimensional structures in bulk water and clusters. Comparison of vibrational spectra with experiments identifies the shell structures and the thermally induced transition from the first to the second shell. We also found intriguing competition between hydration and ion-surface interaction, leading to different solvation dynamics between K and Na. Implications of these results in ionic processes at interfaces are elaborated.

Journal Article↗

Molecular dynamics in the isothermal-isobaric ensemble: the requirement of a "shell" molecule. I. Theory and phase-space analysis.

Current constant pressure molecular-dynamics (MD) algorithms are not consistent with the recent reformulation of the isothermal-isobaric (NpT) ensemble. The NpT ensemble partition function requires the use of a "shell" molecule to identify uniquely the volume of the system, thereby avoiding the redundant counting of configurations [e.g., G. J. M. Koper and H. Reiss, J. Phys. Chem. 100, 422 (1996); D. S. Corti, Phys. Rev. E, 64, 016128 (2001)]. So far, only the NpT Monte Carlo method has been updated to allow the system volume to be defined by a shell particle [D. S. Corti, Mol. Phys. 100, 1887 (2002)]. A shell particle has yet to be incorporated into MD simulations. The proper modification of the NpT MD algorithm is therefore the subject of this paper. Unlike Andersen's method [H. C. Andersen, J. Chem. Phys. 72, 2384 (1980)] where a piston of unknown mass serves to control the response time of volume fluctuations, the newly proposed equations of motion impose a constant external pressure via the introduction of a shell particle of known mass. Hence, the system itself sets the time scales for pressure and volume fluctuations. The new algorithm is subject to a number of fundamentally rigorous tests to ensure that the equations of motion sample phase space correctly. We also show that the Hoover NpT algorithm [W. G. Hoover, Phys. Rev. A. 31, 1695 (1985); 34, 2499 (1986)] does sample phase correctly, but only when periodic boundary conditions are employed.

Journal Article↗

Influence of microbubble shell properties on ultrasound signal: Implications for low-power perfusion imaging.

Low mechanical index perfusion imaging relies on the detection of signals produced by microbubble oscillation at low acoustic powers that results in minimal microbubble destruction. We hypothesized that the optimal acoustic power for real-time imaging would differ for microbubbles with different shell characteristics. Three microbubble agents with varying shell elastic properties according to their polymer composition were studied. Differences in the elastic properties of these microbubbles was demonstrated by: (1) measurement of their bulk modulus and (2) evaluation of their acoustic lability by microscopic visualization of microbubble destruction during insonification at incremental acoustic powers. The ultrasound signal generated by these microbubbles at various mechanical indexes and the degree of microbubble destruction during continuous imaging was determined both in an in vitro flow system and during in vivo imaging in an open-chest canine model. Both studies indicated that optimal power for achieving maximal signal intensity with minimal microbubble destruction was influenced by the shell elastic properties. We conclude that the acoustic power for maximizing acoustic signal without destroying microbubbles during low mechanical index imaging varies according to shell characteristics.

Acoustics↗

Chemically induced supramolecular reorganization of triblock copolymer assemblies: trapping of intermediate states via a shell-crosslinking methodology.

The mechanism of morphological phase transitions was studied for rod-shaped supramolecular assemblies comprised of a poly(acrylic acid)-block-poly(methyl acrylate)-block-polystyrene (PAA(90)-b-PMA(80)-b-PS(100)) triblock copolymer in 33% tetrahydrofuran/water after perturbation by reaction with a positively charged water-soluble carbodiimide. Tetrahydrofuran solvation of the hydrophobic core domain provided the dynamic nature required for the rod-to-sphere phase transition to be complete within 30 min. The intermediate morphologies such as fragmenting rods and pearl-necklace structures were trapped kinetically by the subsequent addition of a diamino crosslinking agent, which underwent covalent crosslinking of the shell layer. Alternatively, shell-crosslinked rod-shaped nanostructures with preserved morphology were obtained by the addition of the crosslinking agent before the addition of the carbodiimide, which allowed for the shell crosslinking to be performed at a faster rate than the morphological reorganization. The formation of robust shell-crosslinked nanostructures provides a methodology by which the morphological evolution processes can be observed, and it allows access to otherwise thermodynamically unstable nanostructures.

Carbodiimides↗