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Morphological and photoelectrochemical characterization of core-shell nanoparticle films for dye-sensitized solar cells: Zn-O type shell on SnO2 and TiO2 cores.

Core-shell type nanoparticles with SnO2 and TiO2 cores and zinc oxide shells were prepared and characterized by surface sensitive techniques. The influence of the structure of the ZnO shell and the morphology ofnanoparticle films on the performance was evaluated. X-ray absorption near-edge structure and extended X-ray absorption fine structure studies show the presence of thin ZnO-like shells around the nanoparticles at low Zn levels. In the case of SnO2 cores, ZnO nanocrystals are formed at high Zn/Sn ratios (ca. 0.5). Scanning electron microscopy studies show that Zn modification of SnO2 nanoparticles changes the film morphology from a compact mesoporous structure to a less dense macroporous structure. In contrast, Zn modification of TiO2 nanoparticles has no apparent influence on film morphology. For SnO2 cores, adding ZnO improves the solar cell efficiency by increasing light scattering and dye uptake and decreasing recombination. In contrast, adding a ZnO shell to the TiO2 core decreases the cell efficiency, largely owing to a loss of photocurrent resulting from slow electron transport associated with the buildup of the ZnO surface layer.

Journal Article↗

Adsorption of oligonucleotides on PMMA/PNIPAM core-shell latexes: polarity of the PNIPAM shell probed by fluorescence.

The adsorption of a rhodamine X labeled oligonucleotide composed of 25-mers of thymine (dT(25)-ROX) onto the thermosensitive shell of PMMA/PNIPAM core-shell latex particles was studied at 22 and 40 degrees C, below and above the T(VPT) (volume phase transition temperature) of the PNIPAM shell, respectively. The experimental binding isotherms were well fitted with the cooperative Hill model. The Hill coefficient is lower than 1 at both temperatures showing that the adsorption is anticooperative. The polarity of the shell was probed by both the lifetimes and solvatochromic shifts of the zwitterionic form of rhodamine X. For temperatures below the shell T(VPT) has a polarity similar to that of water, while for temperatures above the transition the polarity is equivalent to that of a water/dioxane mixture with 30% (v/v) water.

Acrylic Resins↗

Measurement of Cu K-shell and Ag L-shell ionization cross sections by low-energy positron impact.

Inner shell ionization cross sections by low-energy positron impact have been measured. Development of an x-ray detector with thin Si(Li) crystals has enabled the first measurements of the absolute cross sections for the positron impacts in the energy range below 30 keV. Threshold behavior of the measured cross sections for the Cu K shell and Ag L shell are compared with the theoretical results of Gryzinski and Kowalski [Phys. Lett. A 183, 196 (1993)]] and Khare and Wadehra [Can. J. Phys. 74, 376 (1996)]]. Good agreement has been found for the Cu K shell, while the experimental values for the Ag L shell were found to be smaller than the corresponding theoretical results.

Journal Article↗

Plasma levels of cholesterol and testosterone in White Leghorn hens that laid soft-shelled and shell-less eggs.

Plasma concentrations of cholesterol and testosterone were determined in White Leghorn hens that had just laid soft-shelled (SS) or shell-less (SL) eggs and compared to those that laid hard-shelled (HS) eggs. Hens were bled at two different ages, at 22 to 34 and 66 to 74 weeks of age. Blood samples were collected in the morning hours (0600 to 1200 hr) for both age groups with an additional evening bleed (1500 to 1900 hr) for the 66 to 74-week-old hens. Both plasma constituents were higher in hens that laid SS or SL eggs when compared to those which laid HS eggs, but differences were statistically significant only for the 66 to 74-week-old hens bled in the morning hours. The results of this study indicate that elevated levels of testosterone and its precursor, cholesterol, may be related to the production of eggs with little or no shell calcification.

Age Factors↗

Phosphorus phase feeding and uterine and isthmus mucosal enzymes and minerals in relation to soft-shelled and shell-less egg production.

The relationships among phosphorus phase feeding, egg shell quality, and the activities and concentrations of several enzymes and minerals in the uterine and isthmus mucosae of hens at the time of oviposition were investigated. During the first 8 months of production (Phase 1), layer diets contained .3, .5, or .7% available phosphorus. Between 9 and 12 months of production (Phase 2), dietary available phosphorus was either increased or decreased by .2% phosphorus, or was left unchanged. No significant differences due to Phase 1 diets were demonstrated for hard-shelled (HS), soft-shelled (SS), or shell-less (SL) egg production, livability, egg weight, or specific gravity. Phase 2 diets had no significant effect on SS or SL egg production, livability, or egg specific gravity; however, decreasing dietary phosphorus reduced egg weight. Levels as high as .9% had no effect on specific gravity or HS egg production, while .1% dietary phosphorus was detrimental to HS egg production and feed consumption. No significant differences due to dietary available phosphorus or egg type (SS vs. HS) were demonstrated for uterine or isthmus mucosal enzyme activities or mineral contents, with one exception. Higher inorganic phosphorus concentrations were found in the uterus of HS egg layers when compared to levels in the uterus of SS egg layers and the isthmus of HS and SS egg layers. Acid phosphatase and carbonic anhydrase activities, and total calcium levels were significantly higher in the isthmus than the uterus, while alkaline phosphatase and pyrophosphatase activities, and inorganic phosphorus levels were significantly higher in the uterus than the isthmus.(ABSTRACT TRUNCATED AT 250 WORDS)

Acid Phosphatase↗

Relationship of eggshell ultrastructure and shell strength to the soundness of shell eggs.

Factors affecting the soundness of shell eggs are of primary concern to egg processors due to substantial financial losses from cracked and leaker eggs. Ultrastructural analyses were used to examine the palisade layer width and mammillary knob layer thickness of sound, cracked, and leaker eggshells. Subjective observations were also made. There was no significant difference (P > 0.05) in the width of the palisade layer or the mammillary knob layer among sound, cracked, and leaker eggshells. The eggshell strengths of sound, cracked, and leaker eggs were evaluated using puncture force and shell thickness measurements. Sound eggshells were found to have a significantly (P < 0.05) higher mean puncture force (35.3 N) than cracked (30.4 N) and leaker (28.4 N) eggshells. The mean puncture force values for cracked and leaker eggshells were not significantly different from each other (P > 0.05). Regression and correlation analyses indicated a significant correlation (P < 0.01; r = 0.61) between palisade layer width and puncture force. The mean shell thickness values for cracked (0.36 mm) and leaker (0.35 mm) eggs were significantly lower (P < 0.05) than those of sound eggs (0.38 mm), although cracked and leaker eggshell thickness did not differ significantly (P > 0.05). The correlation coefficient between puncture force and shell thickness was significant (P < 0.01; r = 0.56), indicating a possible relationship.

Animals↗

Use of oyster shell as calcium supplement. Part 2. An assessment of the responses of hepatic and serum enzymes, relative organ weights, and bone mineralization in the broiler chicken fed gossypol-containing cottonseed cake supplemented with oyster shell.

The role of oyster shell as calcium supplement in the utilization of gossypol-containing cottonseed cake (CSC) was assessed using Hypeco broiler chickens. The results showed that of the organ measured, only the relative weight of the spleen was significantly (P less than 0.05) decreased by oyster shell supplementation in the CSC diets. Spleen weight correlated negatively (r = -0.45) with dietary calcium. Alkaline phosphatase activity in the liver was significantly (P less than 0.05) increased due to the levels of oyster shell supplemented while the activities of serum and liver alanine aminotransferase and aspartate aminotransferase were not significantly influenced. The results also showed that although oyster shell supplementation generally increased alkaline phosphatase activity, bone mineralization was relatively uninfluenced as judged by the low coefficients of variation (CV) of 3.14-3.51% and 3.39-4.82% for calcium and phosphorus content in the femur and tibia respectively.

Alanine Transaminase↗

The Sextic Centrifugal Distortion Terms for an Open-Shell Complex Consisting of a Diatomic Molecule in a (2S+1)Sigma Electronic State and a Closed-Shell Partner.

An effective Hamiltonian for calculating rotational energy levels of an open-shell diatomic molecule, in a (2S+1)Sigma electronic state, weakly bonded to a closed-shell partner was presented (W. M. Fawzy, J. Mol. Spectrosc. 191, 68-80 (1998)). The Hamiltonian was given as H = H(ev) + H(rot) + H(sr) + H(ss) + H(cd) + H(srcd) + H(sscd), where all the quartic centrifugal distortion correction terms were included in the Hamiltonian term H(cd) but the sextic centrifugal distortion terms were ignored. This Hamiltonian is useful in cases where the complex has a well-defined equilibrium geometry and if the barrier to large-amplitude motion is large compared to the rotational constant of both the closed-shell molecule and its paramagnetic partner; if the barrier to large-amplitude motion is small compared to the rotational constant of one or both of the fragments, then a different treatment is required. In this paper, we introduce the new Hamiltonian terms H(sex(A))(cd) and H(sex(S))(cd), which represent the sextic centrifugal distortion correction terms for an asymmetric rotor. We also introduce all the nonvanishing matrix elements of each of the H(sex(A))(cd) and H(sex(S))(cd) operators. These operators and their matrix elements are required for calculating the rotational energy levels of relatively high J values in the described type of weakly bonded open-shell complexes. The terms H(sex(A))(cd) and H(sex(S))(cd) and their matrix elements are also valid for any stable asymmetric rotor in a nondegenerate electronic state. A brief discussion of the new Hamiltonian terms and their matrix elements is given. Copyright 2000 Academic Press.

Journal Article↗

Esterified astaxanthin levels in lobster epithelia correlate with shell colour intensity: potential role in crustacean shell colour formation.

Carotenoids, particularly astaxanthin, are the primary pigment in crustacean shell colour. Sub-adults of the western rock lobster, Panulirus cygnus, moult from a deep red colour (termed the red phase) to a much paler colour (the white phase) at sexual maturation. We observe a 2.4-fold difference in the amount of total carotenoid present in the shell extracts of reds compared to whites, as might be expected. However, analysis of the underlying epithelium shows that there is no correlation with shell colour and the amount of free (unesterified) astaxanthin-the level of free astaxanthin in reds and whites is not significantly different. Instead, we observe a correlated two-fold difference in the amount of esterified astaxanthin present in the epithelium of red versus white individuals. These data suggest a role for esterified astaxanthin in regulating shell colour formation and suggest that esterification may promote secretion and eventual incorporation of unesterified astaxanthin into the exoskeleton.

Animals↗

Inner-shell ionizations and satellites studied by the open-shell reference symmetry-adapted cluster/symmetry-adapted cluster configuration-interaction method.

Open-shell reference version of the symmetry-adapted cluster (SAC) and SAC-configuration-interaction (CI) methods, termed open-shell reference (OR)-SAC and OR-SAC-CI methods, are developed and applied to inner-shell ionizations of CH4, NH3, H2O, and HF. The inner-shell ionization potentials and spectra calculated by the OR-SAC and OR-SAC-CI methods are in excellent agreement with the experimental data. Including both of the electron correlation and orbital relaxation is important for quantitative agreements. Timing comparisons with the SAC-CI general-R calculations that give similar high accuracies show an efficiency of the present OR-SAC and OR-SAC-CI methods.

Journal Article↗

Quantitative Proteomic Profiling of Pinctada fucata Shell Nacre Defines a Solubility-Based Type Classification of Shell Matrix Proteins.

Shell matrix proteins (SMPs) are key organic components of molluscan biominerals, yet previous nacre proteomics have remained largely qualitative, limiting evaluation of the abundance and fraction association of individual SMPs. Here, we established a quantitative proteomic approach for the nacreous layer of the pearl oyster Pinctada fucata by integrating optimized shell preservation, stepwise fractionation, and data-independent acquisition (DIA) proteomics. SMPs were separated into an ethylenediaminetetraacetic acid (EDTA)-soluble matrix (ESM), an EDTA-insoluble but sodium dodecyl sulfate/dithiothreitol (SDS/DTT)-soluble matrix (SSM), and an SDS/DTT-insoluble matrix (ISM). DIA outperformed data-dependent acquisition in proteome coverage and enabled quantification of 327 SMPs across a broad dynamic range. Fraction-resolved abundance profiling showed that each fraction was characterized by distinct SMP compositions. To summarize these distributions, we introduced a solubility-based type classification that grouped SMPs into four types according to their quantitative partitioning among fractions. Well-known SMPs, including nacrein, Pif 80, and MSI60, were assigned to intuitively consistent types, whereas proteases, protease inhibitors, and tyrosinases also showed biased type distributions. These results support a three-compartment model of the nacreous layer consisting of (i) an insoluble interlamellar membrane core, (ii) a relatively extractable interfacial layer, and (iii) a soluble matrix fraction enriched in proteins potentially involved in ionic regulation and protein maturation. This study provides a quantitative framework for understanding coordinated SMP functions during nacre formation and for comparative analyses of molluscan shell proteomes.

Animals↗

The relationship of dietary levels of phosphorus to the production of soft-shelled and shell-less eggs.

The relationship among available levels of dietary phosphorus (.2, .3, and .4%) and the production of soft-shelled (SS) and shell-less (SL) eggs was investigated in 864 White Leghorns of a commercial strain. An 11-month performance profile included hen-day production of hard-shelled (HS), SS, and SL eggs, feed consumption, livability, egg weight, and specific gravity. Percent HS egg production and feed consumption were significantly lower and egg specific gravity was significantly higher among hens consuming the .2% available phosphorus diet when compared to hens consuming the .3 or .4% available phosphorus diets. The level of available phosphorus in this study did not affect significantly hen livability or the production of SS or SL eggs. Five hours (HS egg in uterus) or 15 hr (SL egg in uterus) prior to expected oviposition time, 1 ml of a 200 mM phosphate solution was injected into the brachial vein (i.v.) or the uterus (i.u.) of hens observed to lay consistently HS eggs. Injections i.v. did not alter expected oviposition time when either a HS or SL egg was in the uterus, but i.u. injections induced premature oviposition when a SL egg was in utero. The concentrations of inorganic phosphorus and total calcium in the plasma and uterine fluid of hens that laid a high or low incidence of SS + SL eggs were determined 5 hr after the egg entered the uterus. Uterine fluid inorganic phosphorus and total calcium and plasma inorganic phosphorus levels of the high and low incidence groups were not significantly different. However, plasma total calcium was significantly higher among high incidence SS + SL layers when compared to low incidence SS + SL layers at this time during the ovulatory cycle.

Animals↗

Relationship of plasma corticosterone and adrenal cholesterol and corticosterone to the production of soft-shelled and shell-less eggs.

Two experiments were conducted to determine if plasma corticosterone and adrenal cholesterol and corticosterone levels differed among hens that laid soft-shelled (SS) or shell-less (SL) eggs when compared with hard-shelled (HS) egg layers. For Experiment 1, four groups of White Leghorn hens were bled at 22 to 34 weeks of age in the morning (0600 to 1200 hr) and at 66 to 74 weeks of age in the morning and evening (1500 to 1900 hr). Group 1 consisted of birds that had just laid SS or SL eggs, whereas Group 2 hens had SS or SL eggs in utero. Groups 3 and 4 represented hens with HS eggs in their uteri and hens that had just laid HS eggs, respectively. For Experiment 2, adrenal cholesterol and corticosterone levels were assayed in high (18+%) and low (0%) incidence SS plus SL egg layers at 73 and 78 weeks of age. Both younger and older hens that laid SS or SL eggs in the morning had similar plasma corticosterone concentrations when compared to HS egg layers. Morning plasma corticosterone levels were significantly higher among hens that laid an egg when compared to hens with eggs in utero, regardless of whether the egg was SS, SL, or HS. However, plasma corticosterone levels of hens producing SS or SL eggs in the evening were significantly higher than levels of hens that laid evening HS eggs. Evening HS egg layers demonstrated the oviposition related peak in plasma corticosterone, but concentrations were 1 ng/ml higher among the evening SS or SL egg layers. Adrenal cholesterol and corticosterone concentrations were similar between high and low incidence SS plus SL layers at either age. It is postulated that evening production of SS or SL eggs is a consequence of elevated plasma corticosterone.

Adrenal Glands↗

Characterization of electrolytes and protein content in isthmic and uterine flushings from hens laying shell-less versus hard-shell eggs.

In Experiment 1, hens laying hard-shell (HS) eggs were sacrificed at each of eight stages of egg formation including oviposition (0 h) and 1, 4, 8, 12, 16, 20, and 24 h after oviposition. In Experiment 2, hens laying either shell-less (SL) or HS eggs were sacrificed at four stages of egg formation (oviposition, 4, 8, and 20 h after oviposition). The isthmus and uterus were flushed with 6 and 10 mL of cold .85% NaCl, respectively, and electrolyte contents were determined. Total flushing contents of calcium, potassium, and magnesium were higher (P less than or equal to .01) in uterine than in isthmic flushings (Experiment 1). In every case, an interaction (P less than or equal to .01) between time of collection and organ (isthmus and uterus) was found, indicating that patterns of change in flushing content of each electrolyte differed in the two organs over time in birds laying HS eggs. In Experiment 2, total recoverable calcium, magnesium, potassium, and total protein were higher in uterine than isthmic flushings (P less than .01). Interactions between time of collection (0, 4, 8, and 20 h) and treatment group (SL or HS) were observed for all electrolytes measured in uterine flushings. Results suggest that calcium, required for shell calcification, does not appear in the isthmic or uterine lumen or both at an appropriate time in SL hens. Thus, production of SL eggs may be related to mechanisms regulating patterns of change or ratios of electrolytes (calcium, magnesium, potassium) or both in the isthmus or uterus of the laying hen.

Animals↗

Noncovalent imprinting in the shell of core-shell nanoparticles.

Propranolol was imprinted using noncovalent interactions in the shell of core-shell nanoparticles prepared by aqueous emulsion polymerization in the presence and absence of toluene. The imprinted particles were characterized, and their capacity to rebind propranolol from both organic and aqueous media was analyzed. Results showed that the amount of template incorporated into the polymer and the presence of toluene as a "porogenic" agent influenced the ability of the nanoparticles obtained to rebind propranolol. The presence of toluene during imprinting increased rebinding by about 2-fold in buffer and by 3-fold in toluene, compared with similar materials made in the absence of toluene during imprinting. It also influenced the final surface area of the particles. Binding site affinity, assessed by radioligand displacement, was measured as IC50 values of about 1-10 microM. This compares with about 3 microM for bulk polymer made with a similar composition. Finally, to demonstrate the advantages of structured particles for analytical applications a new property, fluorescence, was incorporated into the core of the particles without interfering with the imprinted shell and its ability to rebind propranolol.

Journal Article↗

The expression of an engrailed protein during embryonic shell formation of the tusk-shell, Antalis entalis (Mollusca, Scaphopoda).

This study presents the first detailed account of the larval and early post-metamorphic development of a scaphopod species, Antalis entalis, since 1883. Special reference is given to the expression pattern of an engrailed protein during the formation of the embryonic (protoconch) and adult shell (teleoconch). We found that in the trochophore-like larva the engrailed protein is expressed in shell-secreting cells at the margin of the protoconch close to the mantle edge. During metamorphosis the growth of the protoconch and expression of the engrailed protein along its margin stop and the teleoconch starts to form. These data suggest a different genetic background regarding protoconch and teleoconch formation in the Scaphopoda and possibly all Conchifera, thus inferring a different evolutionary origin of both organs. The single anlage of the scaphopod protoconch contradicts earlier hypotheses of a monophyletic taxon Diasoma (Scaphopoda + Bivalvia), which has been mainly based on the assumption of a primarily bilobed shell in both taxa. Comparative data on engrailed expression patterns suggest nervous system patterning as the basic function of engrailedin the Bilateria. However, there are several independent gain-of-function events, namely segment compartmentation in the Annelida and Arthropoda, protoconch formation in the Mollusca, skeletogenesis in the Echinodermata, and limb formation in vertebrates. These findings provide further evidence that homologous genes may act in very different pathways of bilaterian body plan formation in various animal phyla.

Animals↗

Assembly of single-shelled cores and double-shelled virus-like particles after baculovirus expression of major structural proteins P3, P7 and P8 of Rice dwarf virus.

Expression of the core capsid protein P3 of Rice dwarf virus in a baculovirus system resulted in the formation of single-shelled core-like particles in insect cells in the absence of any other capsid proteins. Double-shelled virus-like particles were also observed upon mixing or co-expression of P3 and the major outer capsid protein P8, suggesting that P3 and P8 have the ability to form double-shelled particles both in vivo and in vitro. Core protein P7 expressed in a similar manner was incorporated into the virus-like particles.

Animals↗

p-sd Shell gap reduction in neutron-rich systems and cross-shell excitations in 20 O.

Excited states in 20O were populated in the reaction 10Be(14C,alpha) at Florida State University (FSU). Charged particles were detected with a particle telescope consisting of 4 annularly segmented Si surface barrier detectors and gamma radiation was detected with the FSU gamma detector array. Five new states were observed below 6 MeV from the alpha-gamma and alpha-gamma-gamma coincidence data. Shell model calculations suggest that most of the newly observed states are core-excited 1p-1h excitations across the N=Z=8 shell gap. Comparisons between experimental data and calculations for the neutron-rich O and F isotopes imply a steady reduction of the p-sd shell gap as neutrons are added.

Journal Article↗