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Fabrication of bimodal porous silicate with silicalite-1 core/mesoporous shell structures and synthesis of nonspherical carbon and silica nanocases with hollow core/mesoporous shell structures.

In this work, an attempt has been made to modify the shape and nanostructure of core-shell materials, which have been usually generated on the basis of amorphous spherical cores. Novel core-shell silicate particles, each of which consists of a silicalite-1 zeolite crystal core and mesoporous shell (ZCMS), were synthesized for the first time. The ZCMS core-shell particles are unique because they are of pseudohexagonal prismatic shape and have hierarchical porosity of both a uniform microporous core and a mesoporous shell coexisting in a particle framework. The nonspherical bimodal porous core-shell particles were then utilized as templates to fabricate a new carbon replica structure. Interestingly, the pore replication process was carried out only through the mesopores in the shell, and not through the micropores due to the narrower micropore size in the core, resulting in nonspherical carbon nanocases with a hollow core and mesoporous shell (HCMS) structure. Nonspherical silica nanocases with HCMS structure were also generated by replication using the carbon nanocases as templates, which are not possible to synthesize through other synthetic methods. Interestingly, the pseudohexagonal prismatic shape of the zeolite crystals was transferred onto the carbon and silica nanocases.

Journal Article↗

Modeling shell formation in core-shell nanocrystals in reverse micelle systems.

The mechanisms responsible for the formation of the shell in core-shell nanocrystals are ion-displacement and heterogeneous nucleation. In the ion-displacement mechanism, the shell is formed by the displacement reaction at the surface of the core nanoparticle whereas in heterogeneous nucleation the core particle induces the nucleation (or direct deposition) of shell material on its surface. The formation of core-shell nanocrystals via the post-core route has been examined in the current investigation. A purely probabilistic Monte Carlo scheme for the formation of the shell has been developed to predict the experimental results of Hota et al. (Hota, G.; Jain, S.; Khilar, K. C. Colloids Surf., A 2004, 232, 119) for the precipitation of Ag2S-coated CdS (Ag2S@CdS) nanoparticles. The simulation procedure involves two stages. In the first stage, shell formation takes place as a result of the consumption of supersaturation, ion displacement, and reaction between Ag+ and excess sulfide ions. The growth in the second stage is driven by the coagulation of nanoparticles. The results indicate that the fraction of shell deposited by the ion-displacement mechanism increases with increasing ion ratio and decreases with increasing water-to-surfactant molar ratio.

Journal Article↗

Characterization of shell gland lipids from chickens (Gallus domesticus) producing strong or weak egg shells.

1. The reduction in egg shell strength in hens at the end of the first reproductive cycle was not associated with abnormal uterine or body fat accumulation. 2. The phosphatidylcholine concentration was greater in the shell glands of hens producing strong egg shells compared to that of producing weak egg shells. 3. Differences were not detected in the total lipid or cholesterol concentrations or the fatty acid profiles of phosphatidylcholine or phosphatidylethanolamine fractions. 4. Following an induced molt, the fatty acid profile of the total lipid fraction of the shell gland was altered with a decrease in stearic acid and an increase in oleic acid. 5. The results demonstrate that alterations in egg shell strength are mainly associated with changes in shell gland phospholipid polar head group composition and not with changes in phospholipid fatty acid profile or cholesterol concentration.

Animals↗

Partial shell-filled core-shell tecto(dendrimers): a strategy to surface differentiated nano-clefts and cusps.

Poly(amidoamine) (PAMAM) dendrimer shell reagents possessing either nucleophilic (i.e., primary amines) or electrophilic (i.e., carboxymethyl esters) functional groups have been covalently assembled around appropriate electrophilic or nucleophilic dendrimer core reagents to produce partial shell filled/core-shell tecto(dendrimers). Partial shell-filled products with saturation levels ranging from 28% to 66% were obtained. These metastable, remarkably monodispersed assemblies possess functionally differentiated nano-cusps and clefts that exhibit "autoreactive" behavior. Pacification of these autoreactive products with appropriate alkanolamine reagents produced robust, nonreactive, "hydroxy-amine-differentiated" surfaces that exhibit very active self-assembly properties. Based on the monodispersity, dimensional scaling, and electrophoretic similarities of PAMAM dendrimers to globular proteins, these assemblies may be viewed as crude biomimetics of classical core shell-type protein aggregates. These dimensionally larger, but analogous PAMAM core-shell tecto(dendrimer) architectures extend and complete a similar pattern of autoreactivity and pacification that was observed earlier for traditional mono PAMAM dendrimer core-shell modules possessing unsaturated shell levels.

Chemistry↗

Shell gland adenosine triphosphatase in hens producing strong and weak egg shells.

1. Two groups of 4 hens at the end of their first production cycle were classified as producers of strong egg shells (greater than 70 mg/cm2) and weak egg shells (less than 60 mg/cm2) on the basis of shell surface density. 2. Shell gland mucosa was homogenised and fractionated into nuclear, mitochondrial, microsomal and supernatant fractions, and ATPase activity determined. 3. ATPase activity in the total homogenate was significantly greater for hens producing strong shells (SES) than for hens producing weak shells (WES). 4. ATPase activities detected in the nuclear fraction, mitochondria and microsomes were significantly greater for SES than for WES birds.

Adenosine Triphosphatases↗

Urinary excretion of calcium in the presence or absence of shell formation by chickens producing thick or thin shells.

The pattern of urinary calcium excretion before and during shell formation was observed for White Leghorn chickens producing thick or thin shelled eggs. Urine samples were collected at 2.5, 7.5, 12.5, and 20 hr after oviposition. Urine was collected in a tube inserted to cover both ureters within the cloaca and calcium levels were determined by atomic absorption. Urinary calcium was found to decrease similarly in both shell lines from 44 mg % to 5 to 6 mg % during shell formation. When no shell was being produced, hens of both shell lines excreted calcium in the urine at 34 to 53 mg % levels throughout the 20-hr period.

Animals↗

The relationship of serum calcium to shell weight and other criteria in hens laying a low or high incidence of shell-less eggs.

Experiments were conducted to determine the relationship of serum calcium to shell weight and other criteria. Blood samples for calcium analysis were taken at oviposition in Experiments 1 and 2 from hens fed a 3.5% calcium diet. In Experiment 3, blood was taken at various intervals from hens laying a high or low incidence of shell-less eggs. These hens were fed a control diet or various calcium-deficient diets throughout a 45-day period. No relationship was found between serum calcium and shell weight, or egg weight. Hens laying a high incidence of shell-less eggs showed no decrease in serum calcium or egg production when fed a .58, .25, or .07% calcium diet. However, these criteria were reduced in hens laying a low incidence of shell-less eggs. It was concluded that the normal variation in serum calcium is not related to the hen's ability to produce eggshell. The mechanism of action responsible for cessation of lay when control hens were fed a calcium-deficient diet appeared not to function as it does in hens laying a high incidence of shell-less eggs.

Animals↗

Comparison on pore development of activated carbon produced from palm shell and coconut shell.

A series of experiments were conducted to compare the pore development in palm-shell and coconut-shell-based activated carbons produced under identical experimental conditions. Carbonization and activation processes were carried out at 850 degrees C using a fluidized bed reactor. Within the range of burn-off studied, at any burn-off, the micropore and mesopore volumes created in palm-shell-based activated carbon were always higher than those of coconut-shell-based activated carbon. On macropore volume, for palm-shell-based activated carbon, the volume increased with increase in burn-off up to 30% and then decreased. However, for coconut-shell-based activated carbon, the change in macropore volume with burn-off was almost negligible but the absolute macropore volume decreased with burn-off.

Adsorption↗

Amphiphilic core-shell nanoparticles with poly(ethylenimine) shells as potential gene delivery carriers.

Spherical, well-defined core-shell nanoparticles that consist of poly(methyl methacrylate) (PMMA) cores and branched poly(ethylenimine) shells (PEI) were synthesized via a graft copolymerization of methyl methacrylate from branched PEI induced by a small amount of tert-butyl hydroperoxide. The PMMA-PEI core-shell nanoparticles were between 130 to170 nm in diameter and displayed zeta-potentials near +40 mV at pH 7 in 1 mM aqueous NaCl. Plasmid DNA (pDNA) was mixed with nanoparticles and formed complexes of approximately 120 nm in diameter and was highly monodispersed. The complexes were characterized with respect to their particle size, zeta-potential, surface morphology, and DNA integrity. The complexing ability of the nanoparticles was strongly dependent on the molecular weight of the PEI and the thickness of the PEI shells. The stability of the complexes was influenced by the loading ratio of the pDNA and the nanoparticles. The condensed pDNA in the complexes was significantly protected from enzymatic degradation by DNase I. Cytotoxity studies using MTT colorimetric assays suggested that the PMMA-PEI (25 kDa) core-shell nanoparticles were three times less toxic than the branched PEI (25 kDa). Their transfection efficiencies were also significantly higher. Thus, the PEI-based core-shell nanoparticles show considerable potential as carriers for gene delivery.

Cytotoxicity Tests, Immunologic↗

Food labeling, safe handling statements, labeling of shell eggs; refrigeration of shell eggs held for retail distribution. Food and Drug Administration, HHS. Final rule.

The Food and Drug Administration (FDA) is revising its food labeling regulations to require a safe handling statement on cartons of shell eggs that have not been treated to destroy Salmonella microorganisms. The agency also is requiring that, when held at retail establishments, shell eggs be stored and displayed under refrigeration at a temperature of 7.2 degrees C (45 degrees F) or less. FDA is taking these actions because of the number of outbreaks of foodborne illnesses and deaths caused by Salmonella Enteritidis (SE) that are associated with the consumption of shell eggs. These actions also respond, in part, to petitions from Rose Acres Farm, Inc., and the Center for Science in the Public Interest (CSPI). Safe handling statements will help consumers take measures to protect themselves from illness or deaths associated with consumption of shell eggs that have not been treated to destroy Salmonella (all serotypes). Refrigeration of shell eggs that have not been treated to destroy Salmonella will help prevent the growth of SE in shell eggs.

Consumer Product Safety↗

Serum corticosterone concentrations in developing shell-less and shelled turkey embryos.

1. Turkey embryos grown in shell-less culture (EO) display normal development to day 14 of incubation, after which growth rate is reduced and mortality increases, compared to age-matched in ovo (IO) embryos (Richards 1982. Long term shell-less culture of turkey embryos. Poultry Sci. 61, 2089-2096). 2. In this study serum corticosterone concentrations were monitored in normally incubated embryos and embryos maintained in shell-less culture. 3. On days 14 and 16 of incubation, corticosterone levels were greater (P less than 0.05) in EO than IO embryos, whereas during the later stages corticosterone increased dramatically in the shelled embryos, and remained relatively constant in the EO embryos. 4. EO embryos do not exhibit a pattern of adrenal hormonal secretion that would indicated a stressful condition. 5. The absence of a normal increase in corticosterone in shell-less embryos may contribute to the abnormal embryological development in the later stages of incubation.

Animals↗

Calcium and carbonate supply in the shell gland of hens laying eggs with strong and weak shells and during and after a rest from lay.

The concentration of calcium-binding protein (CaBP) and the activities of calcium adenosine triphosphatase (Ca(2+)-ATPase) and carbonic anhydrase (CA) were determined in the shell gland mucosa of hens in two experiments. In Experiment 1, laying hens on a proprietary layer mash were compared with hens rested from lay by the feeding of whole grain barley. In Experiment 2 comparisons were made of laying hens fed the proprietary layer mash and producing eggs with either strong or weak shells. These latter comparisons were also made when the shell gland was quiescent or active with respect to daily eggshell formation. Feeding whole grain barley reduced egg production to zero after 11 days. This reduction in rate of lay was accompanied by significant reductions in all three markers, the effect on Ca(2+)-ATPase and CaBP being less than for CA. Control values were regained between 10 and 16 days after the barley was replaced with the layer mash. Relative shell strength and the physiological status of the shell gland with respect to time of daily eggshell formation had no significant effect on any marker in Experiment 2.

Animal Feed↗

Relationship between shell porosity, shell thickness, egg weight loss, and embryonic development in Japanese quail eggs.

Japanese quail eggs that hatched (H) or pipped (PIP) exhibited less weight loss through 15 d of incubation than did eggs that died late (LD), whereas eggs containing early dead (ED) embryos exhibited the greatest weight loss. The pore concentration at the large end of each egg was greatest in H eggs when compared with all other types. The pore concentration at the equator was greatest in H eggs and least in the eggs of the ED embryos. All other egg types lay statistically between these two types with regard to equator porosity. The small end pore concentration was similar in H, INF, and LD eggs and in the LD, PIP, and ED eggs. The least number was exhibited by the ED eggs and most by the H eggs. The thinnest shells at the small end were exhibited by H eggs, whereas thicker small end shells were exhibited by ED, LD, and PIP egg types. No differences were observed at the large end or equator. The data suggest that ED eggs exhibit excessive weight loss even though shell porosity was lower and shell thickness was similar to other egg types. This suggests that some functional component of the egg such as the shell membrane or albumen may contribute to this excessive weight loss. A similar statement can be made for LD eggs, which experienced greater weight loss through 15 d than did PIP or H eggs.

Animals↗

Rotational Energy Levels and Line Intensities for 2S+1Sigma-2S+1Sigma Transitions in an Open-Shell Diatomic Molecule Weakly Bonded to a Closed-Shell Partner.

This paper concerns rotational energy levels and line intensities for electronic, vibrational, and microwave transitions in an open-shell complex consisting of an open-shell diatomic molecule and a closed-shell partner. The electronic state of the open-shell diatomic fragment is a 2S+1Sigma state, where S >/= 12, the close-shell partner could be a rare gas atom or a diatomic molecule or a planar polyatomic molecule. We are considering a near-rigid rotor model for a nonlinear complex, taking into account thoroughly all effects of the electron spin and the quartic centrifugal distortion correction terms. The total Hamiltonian is expressed as H=Hrot+Hsr+Hss+Hcd+Hsrcd+Hsscd. We have derived all the nonvanishing matrix elements of the Hamiltonian operators in the molecular basis set. The rotational energy levels are calculated by numerical diagonalization of the total Hamiltonian matrix for each J value. The nonvanishing matrix elements of the electric dipole moment operator are derived in the molecular basis set for electronic, vibrational, and microwave transitions within the complex. Expectation values of the quantum numbers and of the parities of the rotational states are derived in the molecular basis set. Relative intensities of the allowed rotational transitions, expectation values of the quantum numbers and the parities are calculated numerically in the space of the eigenvectors obtained from diagonalization of the Hamiltonian matrix. The formalism and the computer program of this paper are considered as extensions to our previous work [W. M. Fawzy and J. T. Hougen, J. Mol. Spectrosc. 137, 154-165 (1989); W. M. Fawzy, J. Mol. Spectrosc. 160, 84-96 (1993)] and are expected to be particularly useful for analyzing and fitting high-resolution spectra of weakly bonded oxygen complexes. A brief discussion of the Hamiltonian operators, the matrix elements, and the computer program is given. Copyright 1998 Academic Press.

Journal Article↗

Matrix-matched quantitative analysis of trace-elements in calcium carbonate shells by laser-ablation ICP-MS: application to the determination of daily scale profiles in scallop shell (Pecten maximus).

A micro-scale method has been developed for analysis of trace-element concentration profiles in the calcium carbonate shell of the Great Scallop (Pecten maximus). UV laser ablation at 266-nm coupled with ICP-MS detection was used to analyse daily calcite striae of shell samples to obtain high temporal resolution of trace element incorporation. Analysis of scallop shells was carefully examined to determine the quality of calcium carbonate ablation and calibration. An accurate external calibration method based on matrix matching was developed. Twelve sodium-free enriched calcium carbonate standards containing up to twenty-four elements were prepared, by co-precipitation with aqueous ammonia and NH(4)HCO(3), and subsequently back-calibrated in the laboratory. These CaCO(3) standards were found to be homogenous and their use enabled sensitive quantitative analysis (detection limits of a few ng g(-1)) over a wide range of concentrations (0.1 to 500 microg g(-1)). Use of these CaCO(3) standards was also evaluated by analysis of three calcium-rich certified reference materials. Because calibration was consistent with the certified results, this analytical method is a sensitive tool for analysis of environmental calcium carbonate matrices. Repeated analysis of scallop shell samples collected simultaneously at the same location showed that the trace elements are homogeneously distributed along a stria. The reliability of such in-situ records of biogenic calcium carbonate (scallop shells) is apparent from the inter-individual and inter-annual reproducibility of the trace element profiles.

Animals↗

Gaba(A) receptors in the pedunculopontine tegmental nucleus play a crucial role in rat shell-specific dopamine-mediated, but not shell-specific acetylcholine-mediated, turning behaviour.

The role of GABA(A) receptors in the pedunculopontine tegmental nucleus in turning behaviour of rats was studied. Unilateral injection of the GABA(A) receptor agonist, muscimol (25-100 ng), into the pedunculopontine tegmental nucleus dose-dependently produced contraversive pivoting, namely tight head-to-tail turning marked by abnormal hindlimb backward stepping. This effect was GABA(A) receptor specific, since it was prevented by the GABA(A) receptor antagonist, bicuculline (50 ng), which alone did not elicit turning behaviour. Unilateral injection of a mixture of dopamine D(1) ((+/-)-1-phenyl-2,3,4,5-tetrahydro-1H-3-benzazepine-7,8-diol [SKF 38393], 5 microg) and D(2) (quinpirole, 10 microg) receptor agonists into the nucleus accumbens shell has been found to elicit contraversive pivoting, whilst unilateral injection of the acetylcholine receptor agonist (carbachol, 5 microg) into the same site is known to elicit contraversive circling, namely turning marked by normal stepping. The pivoting induced by a mixture of SKF 38393 (5 microg) and quinpirole (10 microg) injected into the nucleus accumbens shell was significantly inhibited by bicuculline (50 ng) injected into the pedunculopontine tegmental nucleus, whereas muscimol (25 ng) had no effect. Neither muscimol (25 ng) nor bicuculline (50 ng) modulated the contraversive circling induced by carbachol (5 microg) injected into the nucleus accumbens shell. It is therefore concluded that unilateral stimulation of GABA(A) receptors in the pedunculopontine tegmental nucleus can elicit contraversive pivoting and that the pedunculopontine tegmental nucleus is one of the output stations of the accumbens region that mediates shell-specific, dopaminergic pivoting, but not of the accumbens region that mediates shell-specific, cholinergic circling.

Acetylcholine↗

The peak CT number of profiles perpendicular to the vertebral cortical shell may be a useful indicator of the integrity of the cortical shell.

Limited spatial resolution affects the ability of clinical CT systems to directly measure the thickness and density of the vertebral cortical shell. In such cases the peak CT number (CTp) of a profile through the cortical shell is approximately proportional to the product of thickness and density and hence an average of several of these values (CTp) may be useful as an indicator of the integrity of the cortical shell. Values of CTp were determined around the anterior two-thirds of the cortical shell of the L3 and L4 lumbar vertebrae of 96 Kuwaiti women (mean age+/-SD=50.0+/-8.5). There was no significant difference between the two vertebrae in terms of CTp and trabecular BMD values. There was a significant correlation between CTp and trabecular BMD for each vertebra (r=0.597, p<0.0001), and between CTp and patient age (r=0.624, p<0.001), suggesting that both cortical and trabecular bone may be subject to similar thinning mechanisms during ageing and osteoporosis. The variation of CTp around the cortical shell, represented by the standard deviation of nine CTp measurements, was significantly correlated with the mean value (r=0.503, p<0.0001) and may be useful as a descriptor of cortical structure.

Adult↗