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PubMed2003

Chemical-mechanical characteristics of crushed oyster-shell.

Enormous amount of oyster-shell waste has been illegally disposed at oyster farm sites along the southern coast of Korea. To seek for a possibility to recycle the waste as construction materials, chemical and mechanical characteristics of crushed oyster-shell were investigated. Chemical and microstructure analyses showed that oyster-shells are predominantly composed of calcium carbonate with rare impurities. Compressive strength tests for soil mortar specimens with varying blending ratio of cement, water, sand, and oyster-shell were compared with normal cement mortar. There was no significant reduction in the compressive strength up to 40% of dosages of oyster-shell instead of sand. The experimental results demonstrate that oyster-shells can be resources of pure calcareous materials and effective in replacement of sand, indicating promising reusable construction materials.

Animals↗

PubMed2003

Mineralogy of shells from two freshwater snails Belgrandiella fontinalis and B kuesteri.

X-ray powder diffraction (XRD) was used to study the mineral composition of shells of snails Belgrandiella fontinalis and Belgrandiella kuesteri collected from three freshwater springs in northeastern Slovenia. The fractions of aragonite, calcite, dolomite and quartz in particular shells were determined. The analysed shells consisted of two or more distinct inorganic layers. The outer shell layer for both species and all sampling localities contained aragonite. The outer layer of B. fontinalis collected at one locality, also contained a small fraction of calcite ( approximately 1 molar%) besides the dominant aragonite. Calcite was identified in the inner layer(s) of both species (2 to 3 molar%), while quartz was found only in B. kuesteri (5-7 molar%). However, both species sampled at one locality showed the presence of dolomite (approx. 20 molar%) in the inner layer(s). The presence of dolomite in the shells of adult gastropods and even molluscs is unusual. A possible formation mechanism and specific ecological factor that could influence the precipitation of dolomite in the shells of different Belgrandiella species is discussed.

Animals↗

PubMedDate not supplied

Graph valence shells as molecular descriptors.

We have introduced a new simple structural descriptor for molecules that is based on the count of the valence shells for vertices in molecular graphs. The construction of the new descriptor is illustrated on 2,3-dimethylhexane and is reported for the 18 octane isomers. The relationship of the new descriptor to the path numbers of a graph is discussed. It can be seen that the path counts and the count of valence of neighbor shells are related for paths of length two (and shells of range two). There is no appreciable correlation between the count of the longer paths and the count of the corresponding neighbor valence shells at larger separations. Use of the neighbor valence shells as molecular descriptors is illustrated on the boiling point, the entropy, and the density of octanes. An intriguing situation is observed for regressions involving considered properties of n-octane isomers C8H18 in that the paths of length two, three, and four and the shells of the range two, three, and four give identical multivariate regression statistics. An explanation for this somewhat unusual aspect of MRA (multiple regression analysis) is offered.

Journal Article↗

PubMed2003

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores.

Gold nanoparticles have been conformally coated with amorphous silica (using a sol-gel method) and then an organic polymer (via surface-grafted, atom transfer radical polymerization) to form spherical colloids with a core-double-shell structure. The thickness of silica and polymer shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the reagent and/or the reaction time. Selective removal of the silica layer (through etching in aqueous HF) led to the formation of hollow polymer beads containing movable gold cores. This new form of core-shell particles provides a unique system for measuring the feature size and transport property associated with hollow particles. In one demonstration, we showed that the thickness of a closed polymer shell could be obtained by mapping the electrons backscattered from the core and shell. In another demonstration, the plasmon resonance band of the gold cores was used as an optical probe to follow the diffusion kinetics of chemical reagents across the polymer shells.

Journal Article↗

PubMed2005

Structure of multiresponsive "intelligent" core-shell microgels.

A doubly temperature-sensitive core-shell microgel composed of two temperature-sensitive polymers with different lower critical solution temperatures (LCSTs) in the core and shell has been studied by small-angle neutron scattering (SANS). The application of a novel universal form factor model in the analysis of the SANS data reveals that the radial density profile at temperatures above the LCSTs of both polymers can be well described by a two-box profile with narrow interfaces. At temperatures between the LCSTs, the radial density profile reveals that the core in the core-shell microgel has larger dimensions than the naked core. Thus the swollen shell pulls the core apart. At temperatures below both LCSTs, however, the shell restricts the core swelling, and the core is found to be smaller than in its native state. This clearly demonstrates the mutual influence of core and shell swelling.

Journal Article↗

PubMed2006

Single quantum dot-micelles coated with silica shell as potentially non-cytotoxic fluorescent cell tracers.

The present study describes a stabilization of single quantum dot (QD) micelles by hydrophobic silica precursors and an extension of the silica layer to form a silica shell around the micelle. The obtained product consists of up to 92% of single nanocrystals (CdSe, CdSe/ZnS, or CdSe/ZnSe/ZnS quantum dots) in the silica micelles, coated with silica shell. The thickness of silica shell could vary, starting from 3 to 4 nm. Increasing the shell thickness increases the photoluminescent characteristics of QDs in aqueous solution. The silica-shelled single CdSe/ZnS QD micelles possess a high quantum yield in aqueous solution, a controlled small size, sharp photoluminescence spectra (fwhm approximately 30 nm), an absence of aggregation, and a high transparency. The presence of a hydrophobic layer between the QD and silica shell ensures an incorporation of other hydrophobic molecules (with interesting properties) in the close proximity of nanocrystal. Thus, it is possible to combine the characteristics of hybrid material with the priority of small size. The nanoparticles are amino functionalized and ready for conjugation. A comparatively good biocompatibility is demonstrated. The nanoparticles show ability for intracellular delivery and are noncytotoxic during long-term incubation with viable cells in the absence of light exposure, which makes them appropriate for cell tracing and drug delivery.

Biocompatible Materials↗

PubMed2005

General equation for size nanocharacterization of the core-shell nanoparticles by X-ray photoelectron spectroscopy.

Nanocharacterization is essential for nanoengineering of new types of core-shell (c-s) nanoparticles, which can be used to design new devices for photonics, electronics, catalysis, medicine, etc. X-ray photoelectron spectroscopy (XPS) has been widely used to study the elemental composition of the c-s nanoparticles. However, the physical and chemical properties of a c-s nanoparticle dramatically depend on the sizes of its core and shell. We therefore propose a general equation for the XPS intensity of a c-s nanoparticle, which is based on an analytical model. With this equation, XPS can now also be used for nanocharacterization of the core and shell sizes of the c-s nanoparticles (with a diameter smaller than or equal to the XPS probing depth of approximately 10 nm). To validate the new equation with experimental XPS data, we first determine the average shell thickness of a group of c-s nanoparticles by comparing the XPS intensity of reference bare cores to that of the c-s nanoparticles. Then we study the growth kinetics of the cores and shells of another group of c-s nanoparticles where the shells are obtained by oxidation.

Nanotechnology↗

PubMed2006

Fabrication and characterization of mesoporous Co3O4 core/mesoporous silica shell nanocomposites.

A mesoporous Co(3)O(4) core/mesoporous silica shell composite with a variable shell thickness of 10-35 nm was fabricated by depositing silica on Co(3)O(4) superlatticed particles. The Brunauer-Emmett-Teller (BET) surface area of the composite with a shell thickness of ca. 2.0 nm was 238.6 m(2)/g, which varied with the shell thickness, and the most frequent pore size of the shell was ca. 2.0 nm. After the shell was eroded with hydrofluoric acid, mesoporous Co(3)O(4) particles with a pore size of ca. 8.7 nm could be obtained, whose BET surface area was 86.4 m(2)/g. It is proposed that in the formation of the composite the electropositive cetyltrimethylammonium bromide (CTAB) micelles were first adsorbed on the electronegative Co(3)O(4) particle surface, which directed the formation of the mesoporous silica on the Co(3)O(4) particle surface. Electrochemical measurements showed that the core/shell composites exhibited a higher discharge capacity compared with that of the bare Co(3)O(4) particles.

Journal Article↗

PubMed2005

Electrochemical and surfaced-enhanced Raman spectroscopic investigation of CO and SCN- adsorbed on Au(core)-Pt(shell) nanoparticles supported on GC electrodes.

Core-shell Au-Pt nanoparticles were synthesized by using a seed growth method and characterized by transmission electron microscopy, X-ray diffraction, and UV-vis spectroscopy. Au(core)-Pt(shell)/GC electrodes were prepared by drop-coating the nanoparticles on clean glassy carbon (GC) surfaces, and their electrochemical behavior in 0.5 M H2SO4 revealed that coating of the Au core by the Pt shell is complete. The electrooxidation of carbon monoxide and methanol on the Au(core)-Pt(shell)/GC was also examined, and the results are similar to those obtained on a bulk Pt electrode. High quality surface-enhanced Raman scattering (SERS) spectra of both adsorbed CO and thiocyanate were observed on the Au(core)-Pt(shell)/GC electrodes. The potential-dependent SERS features resemble those obtained on electrochemically roughened bulk Pt or Pt thin films deposited on roughened Au electrodes. For thiocyanate, the C-N stretching frequency increases with the applied potential, yielding two distinctly different dnu(CN)/dE. From -0.8 to -0.2 V, the dnu(CN)/dE is ca. 50 cm(-1)/V, whereas it is 90 cm(-1)/V above 0 V. The bandwidth along with the band intensity increases sharply above 0 V. At the low-frequency region, Pt-NCS stretching mode at 350 cm(-1) was observed at the potentials from -0.8 to 0 V, whereas the Pt-SCN mode at 280 cm(-1) was largely absent until around 0 V and became dominant at more positive potentials. These potential-dependent spectral transitions were attributed to the adsorption orientation switch from N-bound dominant at the negative potential region to S-bound at more positive potentials. The origin of the SERS activity of the particles is briefly discussed. The study demonstrates a new method of obtaining high quality SERS on Pt-group transition metals, with the possibility of tuning SERS activity by varying the core size and the shell thickness.

Journal Article↗

PubMed2005

Inside-out disruption of silica/gold core-shell nanoparticles by pulsed laser irradiation.

Near-infrared (NIR) femtosecond laser irradiation of metallodielectric core-shell silica-gold (SiO(2)-Au) nanoparticles can induce extreme local heating prior to the rapid dissipation of energy caused by the large surface area/volume ratio of nanometer-scale objects. At low pulse intensities, the dielectric silica core is removed, leaving an incomplete gold shell behind. The gold shells with water inside and out still efficiently absorb NIR light from subsequent pulses, showing that a complete shell is not necessary for absorption. At higher pulse intensities, the gold shell itself is melted and disrupted, leading to smaller, approximately 20-nm gold nanoparticles. Spectroscopic measurements show that this disruption is accompanied by optical hole burning of the peak at 730 nm and formation of a new peak at 530 nm. The silica removal and gold shell disruption confirms significant temperature rise of the core-shall nanoparticle. However, the entire process leads to minimal heating of the bulk solution due to the low net energy input.

Gold↗

PubMed2006

Controlled synthesis of Ag/TiO2 core-shell nanowires with smooth and bristled surfaces via a one-step solution route.

Ag/TiO2 core-shell nanowires were synthesized via a one-step solution method without using a template. Interestingly, the shell morphologies can be controlled to be smooth or bristled by altering the reaction temperature. Moreover, the TiO2 shell thickness and bristle length can be tuned by changing the AgNO3 concentration. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), energy-dispersive X-ray analysis (EDS), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to characterize the resultant Ag/TiO2 core-shell nanowires. Moreover, the absorption peaks of our samples are significantly red-shifted compared with those of the uncoated pure silver nanowires, indicating that interaction between the core and shell occurred. On the basis of the experimental results, we proposed a template-induced Oswald ripening mechanism to explain the formation of the Ag/TiO2 core-shell nanowires.

Journal Article↗

PubMed2006

Imaging the volume transition in thermosensitive core-shell particles by cryo-transmission electron microscopy.

We report a study of colloidal thermosensitive core-shell particles by cryo-transmission electron microscopy (cryo-TEM). The particles consist of a solid core of poly(styrene), onto which a network of cross-linked poly(N-isopropylacrylamide) (PNIPAM) is affixed. In water, the shell of these particles swells when the temperature is low. Raising the temperature above 32 degrees C leads to a marked shrinking of the shell. In this letter, we present the first study of these core-shell particles by cryo-TEM in situ, that is, in aqueous solution. We demonstrate that the core-shell particles are well-defined and exhibit a narrow size distribution. In particular, the PNIPAM shell is compact and has a defined outer surface of a slightly irregular shape. The micrographs show that there are density fluctuations within the network. Cryo-TEM of the system above and below the transition temperature furnishes information about the thermosensitive particles that had not been available through other methods employed in previous investigations.

Journal Article↗

PubMed2006

Fuzzy ternary particle systems by surface-initiated atom transfer radical polymerization from layer-by-layer colloidal core-shell macroinitiator particles.

We report the synthesis of ternary polymer particle material systems composed of (a) a spherical colloidal particle core, coated with (b) a polyelectrolyte intermediate shell, and followed by (c) a grafted polymer brush prepared by surface-initiated polymerization as the outer shell. The layer-by-layer (LbL) deposition process was utilized to create a functional intermediate shell of poly(diallyl-dimethylammonium chloride)/poly(acrylic acid) multilayers on the colloid template with the final layer containing an atom transfer radical polymerization (ATRP) macroinitiator polyelectrolyte. The intermediate core-shell architecture was analyzed with FT-IR, electrophoretic mobililty (zeta-potential) measurements, atomic force microscopy, and transmission electron microscopy (TEM) techniques. The particles were then utilized as macroinitiators for the surface-initiated ATRP grafting process for poly(methyl methacrylate) polymer brush. The polymer grafting was confirmed with thermo gravimetric analysis, FT-IR, and TEM. The polymer brush formed the outermost shell for a ternary colloidal particle system. By combining the LbL and surface-initiated ATRP methods to produce controllable multidomain core-shell architectures, interesting functional properties should be obtainable based on independent polyelectrolyte and polymer brush behavior.

Journal Article↗

PubMed2005

Thermal transport in au-core polymer-shell nanoparticles.

Thermal transport in aqueous suspensions of Au-core polymer-shell nanoparticles is investigated by time-resolved measurements of optical absorption. The addition of an organic cosolvent to the suspension causes the polystyrene component of the polymer shell to swell, and this change in the microstructure of the shell increases the effective thermal conductivity of the shell by a factor of approximately 2. The corresponding time scale for the cooling of the nanoparticle decreases from 200 ps to approximately 100 ps. The threshold concentration of cosolvent that creates the changes in thermal conductivity, 5 vol % tetrahydrofuran in water or 40 vol % N,N-dimethylformamide in water, is identical to the threshold concentrations for producing small shifts in the frequency of the plasmon resonance. Because the maximum fraction of solvent in the polymer shell is less than 20 vol %, the increase in the effective thermal conductivity of the shell cannot be easily explained by contributions to heat transport by the solvent or enhanced alignment of the polystyrene backbone along the radial direction.

Gold↗

PubMed2002

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

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.

Journal Article↗

PubMed2002

Epitaxial core-shell and core-multishell nanowire heterostructures.

Semiconductor heterostructures with modulated composition and/or doping enable passivation of interfaces and the generation of devices with diverse functions. In this regard, the control of interfaces in nanoscale building blocks with high surface area will be increasingly important in the assembly of electronic and photonic devices. Core-shell heterostructures formed by the growth of crystalline overlayers on nanocrystals offer enhanced emission efficiency, important for various applications. Axial heterostructures have also been formed by a one-dimensional modulation of nanowire composition and doping. However, modulation of the radial composition and doping in nanowire structures has received much less attention than planar and nanocrystal systems. Here we synthesize silicon and germanium core-shell and multishell nanowire heterostructures using a chemical vapour deposition method applicable to a variety of nanoscale materials. Our investigations of the growth of boron-doped silicon shells on intrinsic silicon and silicon-silicon oxide core-shell nanowires indicate that homoepitaxy can be achieved at relatively low temperatures on clean silicon. We also demonstrate the possibility of heteroepitaxial growth of crystalline germanium-silicon and silicon-germanium core-shell structures, in which band-offsets drive hole injection into either germanium core or shell regions. Our synthesis of core-multishell structures, including a high-performance coaxially gated field-effect transistor, indicates the general potential of radial heterostructure growth for the development of nanowire-based devices.

Journal Article↗

PubMed2003

Shell shape of the land snail Cornu aspersum in North Africa: unexpected evidence of a phylogeographical splitting.

Anatomical and molecular characters used to differentiate populations of the land snail Cornu aspersum (Helix aspersa) exhibit, in the western Mediterranean, definite and concordant patterns of correlation with geography. Scenarios involving Pliocene geological changes and postglacial expansion during the Pleistocene were proposed in previous studies to account for the establishment of this geographical structure. In the present work, we have performed a spatial analysis of variation in shell morphometrics, after the partitioning of the overall variation into size and shape components by means of a principal component-based approach (Cadima and Jolliffe, 1996). In order to know if the same historical events have also structured shell variation, the analysis includes all the populations from North Africa which were investigated for anatomical and molecular surveys. Contrary to shell size, which shows a significant spatial heterogeneity essentially related to environmental pressures, variation in shell shape components splits the populations according to a geographical pattern reflective of hypotheses suggested for molecular markers and genital anatomy. This implies that the selective forces often invoked to explain spatial changes in shell shape are not the deciding factors in the present case. Moreover, within each of the two geographical clusters defined, Mantel correlograms show that the similarity between populations declines according to an isolation by distance model. Because of the different allometric relationships between shell size and genitalia measurements in Western and Eastern entities of North Africa, mechanical constraints, possibly leading to a precopulatory isolation in the contact zone, are involved.

Africa, Northern↗

PubMed2005

Nonpolar solutes enhance water structure within hydration shells while reducing interactions between them.

The origins of the hydrophobic effect are widely thought to lie in structural changes of the water molecules surrounding a nonpolar solute. The spatial distribution functions of the water molecules surrounding benzene and cyclohexane computed previously from molecular dynamics simulations show a high density first hydration shell surrounding both solutes. In addition, benzene showed a strong preference for hydrogen bonding with two water molecules, one to each face of the benzene ring. The position data alone, however, do not describe the majority of orientational changes in the water molecules in the first hydration shells surrounding these solutes. In this paper, we measure the changes in orientation of the water molecules with respect to the solute through spatial orientation functions as well as radial/angular distribution functions. These data show that the water molecules hydrogen bonded to benzene have a strong orientation preference, whereas those around cyclohexane show a weaker tendency. In addition, the water-water interactions within and between the first two hydration shells were measured as a function of distance and "best" hydrogen bonding angle. Water molecules within the first hydration shell have increased hydrogen bonding structure; water molecules interacting across shell 1 and shell 2 have reduced hydrogen bonding structure.

Benzene↗