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A study of the correlation between organic matrices and nanocomposite materials in oyster shell formation.

Calcium carbonate minerals are an integral part of many organisms. These biogenic minerals are all of original size, shape and high strength, and they are quite different from those found in their abiotic precipitates. It has been accepted that the formation, morphological development and crystallography of the biocomposites are controlled by the intrinsic molecular recognition of macromolecules. In this study, with the analyses of X-ray diffraction and scanning electron microscopy of the texture of biogenic minerals in oyster shells, we noted that the intracrystalline proteins deliberately reduce the coherence lengths of biogenic crystals compared to synthetic ones, leading to more isotropy. In order to understand the exact nature of the controlled nucleation and growth, we investigated the changes in protein conformation in vivo from the mineral-specific layers using Fourier self-deconvolution and Gaussian curve-fitting techniques. And via in vitro assays, we studied the relation of such changes to biomineral phase and morphology. We showed that the shell proteins in vivo are in the higher structural ordered state, and beta-antiparallel structure was predominant in each shell layer. Also, as the shell undergoes a change of calcium carbonate polymorphs from aragonite to calcite, significant alterations of the protein conformation with the denaturing of alpha-helix and beta-structure in the aragonitic layer is induced. These results provide a relationship between the effects of conformational changes on the nanostructure of biocomposites and the necessity of new synthetic strategies.

Animals↗

The use of glaucoma shell tamponade in leaking filtration blebs.

Our experience with the use of glaucoma shell tamponade for bleb leaks in six patients is described. All patients had posterior lip sclerectomies, with leaking blebs diagnosed intraoperatively (2 patients), early (2 patients) and late (2 patients) following surgery. The glaucoma shell works by applying a high resistance to excessive aqueous humor run-off through the leaking wound, and promotes conjunctival epithelial closure by approximating the wound edges. In all six cases the use of the glaucoma shell tamponade was fully effective. The leaks were sealed off and diffuse functioning filtering blebs were maintained, with very low intraocular pressure. We recommend the use of the glaucoma shell tamponade as the treatment of choice for bleb leaks prior to considering surgical repair.

Aged↗

Glutamate and dopamine in nucleus accumbens core and shell: sequence learning versus performance.

This study sought to determine whether neurochemical changes associated with chronic postweaning lead (Pb) exposure, namely, enhanced dopamine (DA) activity and/or blockade of NMDA function in nucleus accumbens (NAC), underlie the learning impairments also associated with this Pb regimen, and whether core or shell subregions of nucleus accumbens would be more important to such effects. If so, then mimicking these neurochemical changes in normal (control) rats should reproduce these Pb-induced learning impairments. For this purpose, the effects of DA (20-80 microg), the non-competitive NMDA antagonist MK-801 (1.0-2.5 microg) or DA+MK-801 (40+1.0, 80+2.5 microg) were infused in core or shell of nucleus accumbens in normal rats and effects on a multiple schedule of repeated learning (RL) and performance (P) evaluated. In core, MK-801 mimicked the effects of Pb exposure, selectively reducing RL accuracy with no corresponding changes in P accuracy, an effect derived from an increased frequency of perseverative errors. DA produced non-specific changes, reducing accuracy levels in RL and P components. Accuracy and rate effects of DA could be reversed by concurrent administration of the higher MK-801 dose. In shell, MK-801, primarily the lower dose, reduced accuracy in both the RL and P components, while DA did not produce any systematic effects. Collectively, these results point to a greater importance of core as compared to shell in the mediation of learning of spatial sequences, and suggest that inhibition of glutamatergic NMDA function may play a critical role in the selective learning impairments associated with chronic low level Pb exposure.

Animals↗

Motor activation by amphetamine infusion into nucleus accumbens core and shell subregions of rats differentially sensitive to dopaminergic drugs.

Selective breeding based on activity in a swim test has been used to produce lines of rats that show a high level of activity in the swim test (Swim High-active (SwHi) rats) and a low level of activity in the swim test (Swim Low-active (SwLo) rats). Previous studies have indicated that dopamine (DA) function is enhanced in SwHi rats and reduced in SwLo rats; a principal finding was that SwLo rats showed much smaller increases in ambulatory activity after systemic administration of amphetamine than did SwHi or non-selected rats. In light of the importance of the nucleus accumbens (NAC) in amphetamine-induced activity, the present study investigated whether DA function in NAC differs in SwHi and SwLo rats. Amphetamine was infused bilaterally into either the core or shell subregion of NAC, and ambulation or swim test activity was then measured. In SwLo rats, infusion of amphetamine (0.2-2.0 microg) into either NAC core or shell produced moderate increases in ambulation. In SwHi rats, infusion of amphetamine into NAC shell produced similar moderate increases in ambulation, but infusion into the core produced markedly larger dose-related increases in ambulation. In the swim test, infusion of amphetamine (1.0 microg) increased activity by affecting the dominant behavior of each line; i.e. struggling increased in SwHi rats and floating decreased in SwLo rats, with large effects seen in both lines with infusion into either NAC core or shell. These results support the idea that the distinct behavioral characteristics of SwHi and SwLo rats are mediated in part by differences in NAC-DA function.

Animals↗

Mutagenic, carcinogenic and cocarcinogenic activity of cashewnut shell liquid.

The petroleum ether extract of cashewnut shell (Anacardium occidentale) was tested for its mutagenic, carcinogenic and cocarcinogenic potency. Mutagenicity tests using Salmonella typhimurium (Ame's test) Strains TA 1535, TA 100 and TA 98 showed that cashewnut shell liquid is non-mutagenic up to a concentration of 0.003% (in 0.1 ml DMSO) with and without metabolic activation (S 9 mixture). Carcinogenicity testing using murine (female Swiss albino mice) two stage skin tumourigenesis model revealed that cashewnut shell liquid has no tumour initiating potency at a concentration of 10% (in 0.2 ml acetone) while it may act as weak promoter (P < 0.05) at a concentration of 5% (in 0.2 ml acetone). Testing for cocarcinogenic potency of cashewnut shell liquid (2% and 5% in 0.2 ml acetone) demonstrated that it has no cocarcinogenic potency on mouse skin tumour model when applied along with 2 x 10(-6)% benzo(a)pyrene in acetone up to a period of 20 weeks.

9,10-Dimethyl-1,2-benzanthracene↗

Production of granular activated carbon from waste walnut shell and its adsorption characteristics for Cu(2+) ion.

Production of granular activated carbon by chemical activation has been attempted employing walnut shells as the raw material. The thermal characteristics of walnut shell were investigated by TG/DTA and the adsorption capacity of the produced activated carbon was evaluated using the titration method. As the activation temperature increased, the iodine value increased. However, a temperature higher than 400 degrees C resulted in a thermal degradation, which was substantiated by scanning electron microscopy (SEM) analysis, and the adsorption capacity decreased. Activation longer than 1h at 375 degrees C resulted in the destruction of the microporous structure of activated carbon. The iodine value increased with the increase in the concentration of ZnCl2 solution. However, excessive ZnCl2 in the solution decreased the iodine value. The extent of activation by ZnCl2 was compared with that by CaCl2 activation. Enhanced activation was achieved when walnut shell was activated by ZnCl2. Applicability of the activated carbon as adsorbent was examined for synthetic copper wastewater. Adsorption of copper ion followed the Freundlich model. Thermodynamic aspects of adsorption have been discussed based on experimental results. The adsorption capacity of the produced activated carbon met the conditions for commercialization and was found to be superior to that made from coconut shell.

Adsorption↗

Differential involvement of dopamine in the shell and core of the nucleus accumbens in the expression of latent inhibition to an aversively conditioned stimulus.

Latent inhibition, the process whereby pre-exposure to a conditioned stimulus without consequence impairs subsequent learning of an association between the conditioned stimulus and an unconditioned stimulus, is reportedly disrupted in both amphetamine-treated rats and in acute schizophrenics. This has led to the suggestion that disruptions in latent inhibition model some of the cognitive impairments associated with hyperactive dopamine transmission as it is expressed in schizophrenic patients. Specifically, fluctuations in dopamine neurotransmission within the nucleus accumbens have been implicated in the mediation of latent inhibition; however, it has not been established whether these dopamine-mediated effects occur in the shell or core subregion of the nucleus. In the present study, 48h after conditioned stimulus-pre-exposed and non-pre-exposed animals experienced 10 pairings of tone and footshock, we measured extracellular levels of dopamine in the shell and core during the expression of latent inhibition to an aversively conditioned tone using in vivo microdialysis. Our results show that pre-exposure to the tone eliminated the conditioned release of dopamine in the shell of the nucleus accumbens and resulted in an attenuated conditioned freezing response to the tone conditioned stimulus. In contrast, dopamine release in the core was not affected by pre-exposure to the tone. These data suggest that it is specifically the shell of the nucleus accumbens in which alterations of dopaminergic tone, whether pharmacologically induced in rodents or the result of disease in humans, may act to disrupt latent inhibition.

3,4-Dihydroxyphenylacetic Acid↗

A microdialysis study of nucleus accumbens core and shell dopamine during operant responding in the rat.

This investigation examined dopamine release and metabolism in nucleus accumbens core and shell during three operant tasks in the rat. Rats were trained to lever press on a fixed-ratio 5, variable-interval 30 s, or a tandem variable interval 30/fixed-ratio 5 schedules; these three schedules were chosen because they generate a wide range of response and reinforcement rates. After several weeks of training, dialysis probes were implanted into nucleus accumbens core or shell subregions. A single 30 min behavioural session was conducted during the dialysis test session. Rats lever pressing on each of the three operant schedules showed a significant increase in extracellular dopamine relative to the food-deprived control group during the behavioural session. In addition, increases in dopamine in nucleus accumbens shell were found to be significantly greater than in the core during the lever pressing period. Across all three schedules, extracellular dopamine in the nucleus accumbens was significantly correlated with the number of lever presses performed, but was not correlated with the number of food pellets delivered. Analysis of covariance, which used amount of food consumed as the covariate, showed an overall group difference, indicating that dopamine levels increased in lever pressing animals even if one corrected for the amount of food consumed. These results indicate that dopamine release was more responsive in the nucleus accumbens shell than in the core during operant responding, and that increases in extracellular dopamine in nucleus accumbens are related to response rate rather than reinforcement magnitude.

Analysis of Variance↗

Effect of magnesium stearate or calcium stearate as additives on dissolution profiles of diltiazem hydrochloride from press-coated tablets with hydroxypropylmethylcellulose acetate succinate in the outer shell.

Effect of magnesium stearate (MgSt) or calcium stearate (CaSt) on the dissolution profiles of diltiazem hydrochloride in the core of press-coated (PC) tablets with an outer shell composed of hydroxypropylmethylcellulose acetate succinate (HPMCAS) was evaluated by porosity and changes in IR spectra of tablets. In JP first fluid (pH 1.2), the lag time increased with decreasing porosity and was greatest by the addition of MgSt to HPMCAS. While, in JP second fluid (pH 6.8), it increased with decreasing porosity by the addition of CaSt, but hardly changed by the addition of MgSt. Thus, using tablets prepared with the same composition as the outer shell, the changes in IR spectra and uptake amount of the dissolution media after immersion in first fluid and second fluid were determined. The results suggested that some physicochemical interaction occur between MgSt and HPMCAS in tablets with HPMCAS and MgSt and the uptake increased markedly in each dissolution medium. These phenomena seem to cause a prolongation of lag time in first fluid but a shortening of it in second fluid in PC tablets with HPMCAS and MgSt. In contrast, CaSt and HPMCAS did not show such interactions and increased the hydrophobic properties of the outer shell. Consequently, the lag time was only slightly prolonged in first fluid, however, markedly prolonged in second fluid due to suppression of second fluid penetration into micro pores in the outer shell and HPMCAS gel formation on the surface in PC tablets with HPMCAS and CaSt.

Antihypertensive Agents↗

Analysis of elastic properties of outer hair cell wall using shell theory(1).

In this study, the mechanical properties of the lateral wall of the outer hair cell (OHC) are determined theoretically. First, the cell is modeled as a cylindrical two-layer shell consisting of the plasma membrane and the cortical lattice. When the stiffness of the plasma membrane is set to be 1.0 mN/m based on the estimated value of Tolomeo et al. [Biophys. J. 71 (1996) 421-429], and Poisson's ratio of the plasma membrane is assumed to be 0.90, the relationships between the stiffness, Poisson's ratio and the orthotropism of the cortical lattice are obtained by comparing the measurement results of cell inflation by Iwasa and Chadwick [J. Acoust. Soc. Am. 92 (1992) 3169-3173] with the numerical ones obtained with our model. Next, the obtained relationships between these mechanical properties of the cell are applied to the model, and the result of the cell length change due to the axial compression measured by Hallworth [J. Neurophysiol. 74 (1995) 2319-2329] is compared with that obtained from our numerical analysis. As a result, the axial and circumferential stiffnesses of the cortical lattice are evaluated to be 4.6 mN/m and 13 mN/m, respectively. Then, the contribution of the cortical lattice to the stiffness of the OHC lateral wall is examined. When the stiffness of the plasma membrane is less than 1.0 mN/m, the mechanical properties of the cortical lattice obtained from the two-layer shell model are nearly the same as those of the cell lateral wall obtained from the one-layer orthotropic shell model. Therefore, it is concluded that the stiffness of the cortical lattice is responsible for that of the whole lateral wall of the OHC. Moreover, the mechanical properties of the OHC obtained in this study are compared with those reported previously, and it is suggested that the one-layer orthotropic shell model is sufficient for further analyses of the motility and force production of the OHC.

Biomechanical Phenomena↗

Cementation of an acetabular liner into a well-fixed acetabular shell during revision total hip arthroplasty.

Cementing a polyethylene liner into a well-fixed acetabular shell during revision hip arthroplasty may be appropriate in select patients. The purpose of this study was to review our early results with this technique. Sixteen patients with >2-year follow-up or who had any complications at <2 years from surgery were identified. Indications for this technique included: failure of the previous locking mechanism, significant polyethylene wear, malposition of the well-fixed metal shell, and previous removal of the liner with a retained acetabular shell. One acetabular shell has been revised at 13 months for multiple dislocations. Hip scores improved an average of 24.2 points. Radiographs revealed no polyethylene dissociation or acetabular loosening. Complications occurred in 7 patients. Initial results appear successful at providing secure fixation, while preventing the bone loss that might occur with removal of a well-fixed component.

Aged↗

Wear of the polyethylene liner-metallic shell interface in modular acetabular components. An in vitro analysis.

The purpose of this study was to determine the effect of compression cycles and wear patterns on the polyethylene liner-metallic shell interface in modular acetabular components. Articular frictional torque was also measured. Modular acetabular components from five manufacturers were tested. The polyethylene liners were sputter coated with gold on the convex surface to enhance the visualization of wear and deformation patterns. Each component was cycled for 10 million cycles in a hydraulic fatigue testing machine. Frictional torque was measured prior to the start of the cyclic loading and in increments of 2 million cycles. Frictional torque was significantly lower in the design with an enhanced polyethylene liner. Abrasion of the gold from the convex surface of polyethylene liners varied from 2 to 23% between designs. Extrusion of the polyethylene into the screw holes in the metallic shells was universal. Three modes of damage (burnishing, punch-out, and gouging) were identified on the convex surface of the polyethylene liner. Abrasion of the gold from the convex surface of the polyethylene varied greatly between designs. This is indicative of relative motion between the polyethylene liner and the metallic shell. This motion must be minimized to limit the generation of wear debris from the convex surface of the polyethylene. Several aspects of modular acetabular component design could be implemented to potentially reduce wear, including limiting the number of holes available for screw placement, smoothing out the edges of the screw holes to avoid punch-out, and avoiding supplemental fixation of the liner unless it is essential to prevent motion between the liner and the metallic shell.

Analysis of Variance↗

Imparting biomimetic ion-gating recognition properties to electrodes with a hydrogen-bonding structured core-shell nanoparticle network.

This paper presents findings of the creation of biomimetic ion-gating properties with core-shell nanoparticle network architectures. The architectures were formed by hydrogen-bonding linkages via an exchange-cross-linking-precipitation reaction pathway using gold nanoparticles capped with thiolate shell and alkylthiols terminated with carboxylic groups as model building blocks. Such network assemblies have open frameworks in which void space is in the form of a channel or chamber with the nanometer-sized cores defining its size, the geometric arrangement defining its shape, and the shell structures defining its chemical specificity. The formation of the network linkages via head-to-head hydrogen-bonded carboxylic terminals and the reversible pH-tuned structural properties between neutral and ionic states were characterized using infrared reflectance spectroscopic technique. The biomimetic ion-gating properties were demonstrated by measuring the pH-tuned network "open-close" responses to charged redox probes. Such redox responses were shown to depend on the degree of protonation-deprotonation of carboxylic groups at the interparticle linkages, core sizes of the nanoparticles, and charges of the redox probes. Differences in structural networking, pH-tuning, and electrochemical gating properties were identified between the network films derived from nanoparticles of two different core sizes (2 and 5 nm). The mechanistic correlation of these structural properties was discussed. These findings have added a new pathway to the current approaches to biomimetic molecular recognition via design of core-shell nanoparticle architectures at both nanocrystal and molecular scales.

Alum Compounds↗

The vault exterior shell is a dynamic structure that allows incorporation of vault-associated proteins into its interior.

Vaults are 13 million Da ribonucleoprotein particles with a highly conserved structure. Expression and assembly by multimerization of an estimated 96 copies of a single protein, termed the major vault protein (MVP), is sufficient to form the minimal structure and entire exterior shell of the barrel-shaped vault particle. Multiple copies of two additional proteins, VPARP and TEP1, and a small untranslated vault RNA are also associated with vaults. We used the Sf9 insect cell expression system to form MVP-only recombinant vaults and performed a series of protein-mixing experiments to test whether this particle shell is able to exclude exogenous proteins from interacting with the vault interior. Surprisingly, we found that VPARP and TEP1 are able to incorporate into vaults even after the formation of the MVP vault particle shell is complete. Electrospray molecular mobility analysis and spectroscopic studies of vault-interacting proteins were used to confirm this result. Our results demonstrate that the protein shell of the recombinant vault particle is a dynamic structure and suggest a possible mechanism for in vivo assembly of vault-interacting proteins into preformed vaults. Finally, this study suggests that the vault interior may functionally interact with the cellular milieu.

Animals↗

Layer-by-layer engineering of biocompatible, decomposable core-shell structures.

The objective of the present investigation was to fabricate composite colloidal particles consisting of a sacrificial, decomposable template of biodegradable nature covered with biocompatible polyelectrolyte multilayers using the layer-by-layer sequential adsorption technique. Poly-dl-lactic acid and poly(dl-lactic-co-glycolic acid) were chosen to design the microparticulate template, and a preliminary feasibility study was carried out with poly(styrene sulfonate sodium)-poly(allylamine hydrochloride) as shell components. The properties of both core-shell and hollow structures obtained by core dissolution were characterized by confocal laser scanning microscopy, microelectrophoresis, scanning force microscopy, and scanning electron microscopy. The concept was then extended to biocompatible polyelectrolytes as shell wall building blocks to deduce stable hollow capsules with tailored properties. Uniform, complete coating with oppositely charged polyelectrolyte pairs was achieved for all the combinations investigated. The results demonstrate that polyester microparticles could serve as viable alternative components to conventionally employed templates to derive hollow capsules with defined size, shape, and shell thickness. With all the components used for fabrication being biocompatible, these polyelectrolyte capsules may find interesting applications in the fields of biology, biochemistry, biotechnology, and drug delivery.

Biocompatible Materials↗

Definitive evidence for the contribution of biradical character in a closed-shell molecule, derivative of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene.

This study provides conclusive proof that the thermally excited open-shell state with biradical character is contributing to the ground state of a closed-shell molecule, tF-BDPI-2Y, where four hydrogen atoms at the central phenylene ring are substituted with four fluorine atoms of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene (BDPI-2Y). A small increase in the population of biradical species of tF-BDPI-2Y results in the formation of the dimer form by the radical recombination reaction. Controlling the equilibrium between a closed-shell diamagnetic-quinoid state and an open-shell paramagnetic-biradical state will provide significant progress in the field of pi-conjugated delocalized biradical chemistry.

Journal Article↗

Characterization of superparamagnetic "core-shell" nanoparticles and monitoring their anisotropic phase transition to ferromagnetic "solid solution" nanoalloys.

The structure, magnetism, and phase transition of core-shell type CoPt nanoparticles en route to solid solution alloy nanostructures are systematically investigated. The characterization of Co(core)Pt(shell) nanoparticles obtained by a "redox transmetalation" process by transmission electron microscopy (TEM) and, in particular, X-ray absorption spectroscopy (XAS) provides clear evidence for the existence of a core-shell type bimetallic interfacial structure. Nanoscale phase transitions of the Co(core)Pt(shell) structures toward c-axis compressed face-centered tetragonal (fct) solid solution alloy CoPt nanoparticles are monitored at various stages of a thermally induced annealing process and the obtained fct nanoalloys show a large enhancement of their magnetic properties with ferromagnetism. The relationship between the nanostructures and their magnetic properties is in part elucidated through the use of XAS as a critical analytical tool.

Journal Article↗

Multiwall carbon nanotubes made of monochirality graphite shells.

A multiwall carbon nanotube (MWCNT) consists of several or many concentric carbon shells, each of which could be metallic or semiconducting. Both theoretical predictions and experimental results suggest that MWCNTs have exotic electronic structures and intriguing transport properties, which are highly dependent on chirality of each shell. However, the structural defects and the random distribution of chirality of each concentric graphitic shell make the MWCNTs difficult for basic research and technological applications. Thus far, it is still a challenge to get the high crystalline MWCNTs with limited atomic conformation. Here, we report the synthesis of high crystalline MWCNTs made of monochirality graphite shells by a low-temperature chemical vapor deposition (CVD) process in plasma environment. Structural analysis, carried out by transmission electron microscopy (TEM) image and electron diffraction methods, reveal that the MWCNTs are well-crystallized and that most of them have nearly identical chiralities.

Journal Article↗