On the cytotoxicity of carbon nanotubes

The cytotoxicity of carbon nanotubes (CNTs) is a major concern today well before its unusual physicochemical, mechanical, and electrical properties are fully exploited for commercial interests and subsequent mass production leading to greater possibilities for its exposure to humans and the environment. Contradictory reports on cytotoxicity of CNTs often appear in the literature and a mechanistic explanation of the reported toxicity remains obscure. We review here the conflicting results to focus categorically on an array of issues in CNT cytotoxicity. They include dispersion, aggregation status, coating or functionalization and immobilization, cellular uptake or internalization, purity in terms of metal catalyst contaminants, size and size distribution, surface area, surface chemistry and surface reactivity, cell types selected for experimentation as well as bioassay of nanotoxicity itself attesting as an issue in cytotoxicity. Recently a general agreement has emerged towards the potential toxicity of CNTs, although various paradigms explaining the mechanisms of CNT cytotoxicity continue to be elusive in the literature. A lack of synergy among various issues while studying cytotoxicity and most developed paradigms for the mechanism of CNT toxicity is highlighted.

Identifying the financial barriers to deliberative, affordable apartment development in Australia

Purpose The purpose of this paper is to identify the financial barriers to the supply of affordable apartments in Australia and examine whether demand aggregation and ‘deliberative development’ (self-build) can form a new affordable housing ‘structure of provision’. Design/methodology/approach Market design, an offshoot of game theory, is used to analyse the existing apartment development model, with ‘deliberative development’ proposed as an innovative alternative. Semi-structured interviews with residential development financiers are used to evaluate whether deliberative development could obtain the requisite development finance. Findings Our investigation into the financial barriers of a deliberative development model suggest that while there are hurdles, these can be addressed if key risks in the exchange process can be mitigated. Hence, affordability can be enhanced by ‘deliberative development’ replacing the existing speculative development model. Research implications Market design is a new innovative theoretical approach to understanding the supply of housing, offering practical solutions to affordable apartment supply in Australia. Originality/value This research identifies financial barriers to the supply of affordable apartments; introduces theoretical understandings gained from market design as an innovative solution; provides evidence that a new structure of building provision based on ‘deliberative development’ could become a key means of achieving more affordable and better designed apartments.

Impressive Gelation in Organic Solvents by Synthetic, Low Molecular Mass, Self-Organizing Urethane Amides of L-Phenylalanine

Synthetic routes leading to 12 L-phenylalanine based mono- and bipolar derivatives (1-12) and an in-depth study of their structure-property relationship with respect to gelation have been presented. These include monopolar systems such as N-[(benzyloxy)carbonyl]-L-phenylalanine-N-alkylamides and the corresponding bipolar derivatives with flexible and rigid spacers such as with 1,12-diaminododecane and 4,4'-diaminodiphenylmethane, respectively. The two ends of the latter have been functionalized with N-[(benzyloxy)carbonyl]-L-phenylalanine units via amide connection. Another bipolar molecule was synthesized in which the middle portion of the hydrocarbon segment contained polymerizable diacetylene unit. To ascertain the role of the presence of urethane linkages in the gelator molecule protected L-phenylalanine derivatives were also synthesized in which the (benzyloxy)carbonyl group has been replaced with (tert-butyloxy)carbonyl, acetyl, and benzoyl groups, respectively. Upon completion of the synthesis and adequate characterization of the newly described molecules, we examined the aggregation and gelation properties of each of them in a number of solvents and their mixtures. Optical microscopy and electron microscopy further characterized the systems that formed gels. Few representative systems, which showed excellent gelation behavior was, further examined by FT-IR, calorimetric, and powder X-ray diffraction studies. To explain the possible reasons for gelation, the results of molecular modeling and energy-minimization studies were also included. Taken together these results demonstrate the importance of the presence of (benzyloxy)carbonyl unit, urethane and secondary amide linkages, chiral purities of the headgroup and the length of the alkyl chain of the hydrophobic segment as critical determinants toward effective gelation.

Index properties of illite-bentonite mixtures in electrolyte solutions

Bentonite, commonly used for liner constructions in waste containment systems, possesses many limitations. Illite or illite containing bentonite has been proposed as an alternative material for liner construction. Their properties in different types of pore fluids are important to assess the long-term performance of the liner. Further, the illite-bentonite interaction occurs and changes their properties. The effect of these interactions is known when the pore fluid is only water. How their properties are modified in electrolyte solutions has been brought out in this paper. The index properties have been studied since they give an indication of their engineering properties. Due to reduction in the thickness of the diffused double layer and consequent particle aggregation in bentonite, the effect of clay-clay interaction reduces in electrolyte solutions. In electrolyte solutions, the liquid limit, the plasticity index, and free swell index of bentonite are lower than illite. The plasticity index of bentonite is further reduced in KCI solution. Clays with a higher plasticity index perform better to retain pollutants and reduce permeability. Hence, the presence of both illite and bentonite ensures better performance of the liner in different fluids.

Intercellular Communication in the Multicellular Stage of Dictyostelium-Discoideum

The aim of the present study was to draw inferences regarding the properties of single cells responsible for co-operative behaviour in the slug of the soil amoeba Dictyostelium discoideum. The slug is an integrated multicellular mass formed by the aggregation of starved cells. The amoebae comprising the slug differentiate according to their spatial locations relative to one another, implying that, as in the case of other regulative embryos, they must be in mutual communication. We have previously shown that one manifestation of this communication is the time taken for the anteriormost fragment of the slug, the tip, to regenerate from slugs which have been rendered tipless by amputation. We present results of tip-regeneration experiments performed on genetically mosaic slugs. By comparing the mosaics with their component pure genotypes, we were able to discriminate between a set of otherwise equally plausible modes of intercellular signalling. Neither a'pacemaker' model, in which the overall rate of tip regeneration is determined by the cell with the highest frequency of autonomous oscillation, nor an 'independent-particle' model, in which the rate of regeneration is the arithmetical average of independent cell-dependent rates, is in quantitative accord with our findings. Our results are best explained by a form of signalling which operates by means of cell-to-cell relay. Therefore intercellular communication Seems to be essential for tip regeneration.

x-ray studies on crystalline complexes involving amino-acids and peptides .10. head-to-tail sequences in the crystal-structure of l-lysine acetate

l-Lysine acetate crystallises in the monoclinic space group P21 with a = 5.411 (1), b = 7.562(1), c= l2.635(2) Å and β = 91.7(1). The crystal structure was solved by direct methods and refined to an R value of 0.049 using the full matrix least squares method. The conformation and the aggregation of lysine molecules in the structure are similar to those found in the crystal structure of l-lysine l-aspartate. A conspicuous similarity between the crystal structures of l-arginine acetate and l-lysine acetate is that in both cases the strongly basic side chain, although having the largest pK value, interacts with the weakly acidic acetate group leaving the α-amino and the α-carboxylate groups to take part in head-to-tail sequences. These structures thus indicate that electrostatic effects are strongly modulated by other factors so as to give rise to head-to-tail sequences which have earlier been shown to be an almost universal feature of amino acid aggregation in the solid state.

External signal-activated liposomal drug delivery systems

Modern drug discovery gives rise to a great number of potential new therapeutic agents, but in some cases the efficient treatment of patient may not be achieved because the delivery of active compounds to the target site is insufficient. Thus, drug delivery is one of the major challenges in current pharmaceutical research. Numerous nanoparticle-based drug carriers, e.g. liposomes, have been developed for enhanced drug delivery and targeting. Drug targeting may enhance the efficiency of the treatment and, importantly, reduce unwanted side effects by decreasing drug distribution to non-target tissues. Liposomes are biocompatible lipid-based carriers that have been studied for drug delivery during the last 40 years. They can be functionalized with targeting ligands and sensing materials for triggered activation. In this study, various external signal-assisted liposomal delivery systems were developed. Signals can be used to modulate drug permeation or release from the liposome formulation, and they provide accurate control of time, place and rate of activation. The study involved three types of signals that were used to trigger drug permeation and release: electricity, heat and light. Electrical stimulus was utilized to enhance the permeation of liposomal DNA across the skin. Liposome/DNA complex-mediated transfections were performed in tight rat epidermal cell model. Various transfection media and current intensities were tested, and transfection efficiency was evaluated non-invasively by monitoring the concentration of secreted reporter protein in cell culture medium. Liposome/DNA complexes produced gene expression, but electrical stimulus did not enhance the transfection efficiency significantly. Heat-sensitive liposomal drug delivery system was developed by coating liposomes with biodegradable and thermosensitive poly(N-(2-hydroxypropyl) methacrylamide-mono/dilactate polymer. Temperature-triggered liposome aggregation and contents release from liposomes were evaluated. The cloud point temperature (CP) of the polymer was set to 42 °C. Polymer-coated liposome aggregation and contents release were observed above CP of the polymer, while non-coated liposomes remained intact. Polymer precipitates above its CP and interacts with liposomal bilayers. It is likely that this induces permeabilization of the liposomal membrane and contents release. Light-sensitivity was introduced to liposomes by incorporation of small (< 5 nm) gold nanoparticles. Hydrophobic and hydrophilic gold nanoparticles were embedded in thermosensitive liposomes, and contents release was investigated upon UV light exposure. UV light-induced lipid phase transitions were examined with small angle X-ray scattering, and light-triggered contents release was shown also in human retinal pigment epithelial cell line. Gold nanoparticles absorb light energy and transfer it into heat, which induces phase transitions in liposomes and triggers the contents release. In conclusion, external signal-activated liposomes offer an advanced platform for numerous applications in drug delivery, particularly in the localized drug delivery. Drug release may be localized to the target site with triggering stimulus that results in better therapeutic response and less adverse effects. Triggering signal and mechanism of activation can be selected according to a specific application.

Population structure, mortality and growth of Pinna nobilis Linnaeus, 1758 (Mollusca, Bivalvia) at different depths in Moraira bay (Alicante, Western Mediterranean)

An investigation to characterize the causes of Pinna nobilis population structure in Moraira bay (Western Mediterranean) was developed. Individuals of two areas of the same Posidonia meadow, located at different depths (A1, -13 and A2, -6 m), were inventoried, tagged, their positions accurately recorded and monitored from July 1997 to July 2002. On each area, different aspects of population demography were studied (i.e. spatial distribution, size structure, displacement evidences, mortality, growth and shell orientation). A comparison between both groups of individuals was carried out, finding important differences between them. In A1, the individuals were more aggregated and mean and maximum size were higher (A1, 10.3 and A2, 6 individuals/100 m(2); A1, x = 47.2 +/- 9.9; A2, x = 29.8 +/- 7.4 cm, P < 0.001, respectively). In A2, growth rate and mortality were higher, the latter concentrated on the largest individuals, in contrast to A1, where the smallest individuals had the higher mortality rate [A1, L = 56.03(1 - e(-0.17t)); A2, L = 37.59(1 - e(-0.40t)), P < 0.001; mean annual mortality A1: 32 dead individuals out of 135, 23.7% and A2: 16 dead individuals out of 36, 44.4%, and total mortality coefficients (z), z(A1(-30)) = 0.28, z(A1(31-45)) = 0.05, z(A1(46-)) = 0.08; z(A2(-30)) = 0.15, z(A2(31-45)) = 0.25]. A common shell orientation N-S, coincident with the maximum shore exposure, was observed in A2. Spatial distribution in both areas showed not enough evidence to discard a random distribution of the individuals, despite the greater aggregation on the deeper area (A1) (A1, chi(2) = 0.41, df = 3, P > 0.5, A2, chi(2)= 0.98, df = 2 and 0.3 < P < 0.5). The obtained results have demonstrated that the depth-related size segregation usually shown by P. nobilis is mainly caused by differences in mortality and growth among individuals located at different depths, rather than by the active displacement of individuals previously reported in the literature. Furthermore, dwarf individuals are observed in shallower levels and as a consequence, the relationship between size and age are not comparable even among groups of individuals inhabiting the same meadow at different depths. The final causes of the differences on mortality and growth are also discussed.

Effects of fish density distribution and effort distribution on catchability

The effects of fish density distribution and effort distribution on the overall catchability coefficient are examined. Emphasis is also on how aggregation and effort distribution interact to affect overall catch rate [catch per unit effort (cpue)]. In particular, it is proposed to evaluate three indices, the catchability index, the knowledge parameter, and the aggregation index, to describe the effectiveness of targeting and the effects on overall catchability in the stock area. Analytical expressions are provided so that these indices can easily be calculated. The average of the cpue calculated from small units where fishing is random is a better index for measuring the stock abundance. The overall cpue, the ratio of lumped catch and effort, together with the average cpue, can be used to assess the effectiveness of targeting. The proposed methods are applied to the commercial catch and effort data from the Australian northern prawn fishery. The indices are obtained assuming a power law for the effort distribution as an approximation of targeting during the fishing operation. Targeting increased catchability in some areas by 10%, which may have important implications on management advice.

A H-1-NMR STUDY OF BILIRUBIN IX-ALPHA SOLUBILIZATION BY CHOLATE MICELLES - APPLICATION OF NUCLEAR OVERHAUSER EFFECTS

The solubilization of bilirubin IX-Alpha in aqueous solution by sodium cholate micelles has been examined by 270 MHz 1H-NMR spectroscopy. Incorporation of bilirubin into the micelles is accompanied by specific shifts of bilirubin vinyl and bridgehead protons and the C18 and C19 methyl groups of the steroid. The observed chemical shifts show a monotonic concentration dependence suggesting that changes in aggregation size are continuous. Nuclear Overhauser effects (NOE) have been shown to be a useful probe or micellization. A 4:1 cholate/bilirubin mixture has been investigated by difference NOE spectroscopy. The observation of intermolecular nuclear Overhauser effects between peripheral protons of bilirubin and cholate are diagnostic of spatially proximate groups. Inter-cholate nuclear Overhauser effects increase in magnitude upon bilirubin incorporation suggesting closer packing of steroid molecules on solubilization of the pigment. Intramolecular nuclear Overhauser effects observed for solubilized bilirubin are consistent with a compact intramolecularly hydrogen-bonded conformation resembling that determined for bilirubin in the solid state.

Perylene-based profluorescent nitroxides for the rapid monitoring of polyester degradation upon weathering: An assessment

A profluorescent nitroxide possessing an isoindoline nitroxide moiety linked to a perylene fluorophore was developed to monitor radical mediated degradation of melamine-formaldehyde crosslinked polyester coil coatings in an industry standard accelerated weathering tester. Trapping of polyester-derived radicals (most likely C-radicals) that are generated during polymer degradation leads to fluorescent closed-shell alkoxy amines, which was used to obtain time-dependent degradation profiles to assess the relative stability of different polyesters towards weathering. The nitroxide probe couples excellent thermal stability and satisfactory photostability with high sensitivity and enables detection of free radical damage in polyesters under conditions that mimic exposure to the environment on a time scale of hours rather than months or years required by other testing methods. There are indications that the profluorescent nitroxide undergoes partial photo-degradation in the absence of polymer-derived radicals. Unexpectedly, it was also found that UV-induced fragmentation of the NO–C bond in closed-shell alkoxy amines leads to regeneration of the profluorescent nitroxide and the respective C-radical. The maximum fluorescence intensity that could be achieved with a given probe concentration is therefore not only determined by the amount of polyester radicals formed during accelerated weathering, but also by the light-driven side reactions of the profluorescent nitroxide and the corresponding alkoxy amine radical trapping products. Studies to determine the optimum probe concentration in the polymer matrix revealed that aggregation and re-absorption effects lowered the fluorescence intensity at higher concentrations of the profluorescent nitroxide, but too low probe concentrations, where these effects would be avoided, were not sufficient to trap the amount of polyester radicals formed upon weathering. The optimized experimental conditions were used to assess the impact of temperature and UV irradiance on polymer degradation during accelerated weathering.

Modeling the role of competition and cooperation in the evolution of katydid acoustic synchrony

The precise timing of individual signals in response to those of signaling neighbors is seen in many animal species. Synchrony is the most striking of the resultant timing patterns. One of the best examples of acoustic synchrony is in katydid choruses where males produce chirps with a high degree of temporal overlap. Cooperative hypotheses that speculate on the evolutionary origins of acousti synchrony include the preservation of the species-specific call pattern, reduced predation risks, and increased call intensity. An alternative suggestion is that synchrony evolved as an epiphenomenon of competition between males in response to a female preference for chirps that lead other chirps. Previous models investigating the evolutionary origins of synchrony focused only on intrasexual competitive interactions. We investigated both competitive and cooperative hypotheses for the evolution of synchrony in the katydid Mecopoda ``Chirper'' using physiologically and ecologically realistic simulation models incorporating the natural variation in call features, ecology, female preferences, and spacing patterns, specifically aggregation. We found that although a female preference for leading chirps enables synchronous males to have some selective advantage, it is the female preference for the increased intensity of aggregations of synchronous males that enables synchrony to evolve as an evolutionarily stable strategy.

Role of Diadegma semiclausum (Hymenoptera: Ichneumonidae) in controlling Plutella xylostella (Lepidoptera: Plutellidae): Cage exclusion experiments and direct observation

We evaluated the role of the larval parasitoid, Diadegma semiclausum Hellén (Hymenoptera: Ichneumonidae), in controlling Plutella xylostella (L.) (Lepidoptera: Plutellidae) by cage exclusion experiments and direct field observation during the winter season in southern Queensland, Australia. The cage exclusion experiment involved uncaged, open cage and closed cage treatments. A higher percentage (54-83%) of P. xylostella larvae on sentinel plants were lost in the uncaged treatment than the closed (4-9%) or open cage treatments (11-29%). Of the larvae that remained in the uncaged treatment, 72-94% were parasitized by D. semiclausum, much higher than that in the open cage treatment (8-37% in first trial, and 38-63% in second trial). Direct observations showed a significant aggregation response of the field D. semiclausum populations to high host density plants in an experimental plot and to high host density plots that were artificially set-up near to the parasitoid source fields. The degree of aggregation varied in response to habitat quality of the parasitoid source field and scales of the manipulated host patches. As a result, density-dependence in the pattern of parasitism may depend on the relative degree of aggregation of the parasitoid population at a particular scale. A high degree of aggregation seems to be necessary to generate density-dependent parasitism by D. semiclausum. Integration of the cage exclusion experiment and direct observation demonstrated the active and dominant role of this parasitoid in controlling P. xylostella in the winter season. A biologically based IPM strategy, which incorporates the use of D. semiclausum with Bt, is suggested for the management of P. xylostella in seasons or regions with a mild temperature.

Pheromone-mediated mass trapping and population diversion as strategies for suppressing Carpophilus spp. (Coleoptera: Nitidulidae) in Australian stone fruit orchards

1 Five experiments were conducted during 1995-99 in stone fruit orchards on the Central Coast and in inland New South Wales, Australia, on the use of synthetic aggregation pheromones and a coattractant to suppress populations of the ripening fruit pests Carpophilus spp. (Coleoptera: Nitidulidae). 2 Perimeter-based suppression traps baited with pheromone and coattractant placed at 3m intervals around small fruit blocks, caught large numbers of Carpophilus spp. Very small populations of Carpophilus spp. occurred within blocks, and fruit damage was minimal. 3 Carpophilus spp. populations in stone fruit blocks 15-370m from suppression traps were also small and non-damaging, indicating a large zone of pheromone attractivity. 4 Pheromone/coattractant-baited suppression traps appeared to divert Carpophilus spp. from nearby (130 m) ripening stone fruit. Ten metal drums containing decomposing fruit, baited with pheromone and treated with insecticide, attracted Carpophilus spp. and appeared to reduce populations and damage to ripening fruit at distances of 200-500 m. Populations and damage were significantly greater within 200m of the drums and may have been caused by ineffective poisoning or poor quality/overcrowding of fruit resources in the drums. 5 Suppression of Carpophilus spp. populations using synthetic aggregation pheromones and a coattractant appears to be a realistic management option in stone fruit orchards. Pheromone-mediated diversion of beetle populations from ripening fruit may be more practical than perimeter trapping, but more research is needed on the effective range of Carpophilus pheromones and the relative merits of trapping compared to attraction to insecticide-treated areas.

Efficacy of multispecies pheromone lures for Carpophilus davidsoni Dobson and Carpophilus mutilatus Erichson (Coleoptera: Nitidulidae)

Orchard experiments were conducted in southern New South Wales to evaluate the efficacy of multispecies pheromone lures in trapping two economically important species of Carpophilus. Captures of Carpophilus davidsoni Dobson and Carpophilus mutilatus Erichson in traps baited with aggregation pheromones of both species or a three-way lure that also included the pheromone of Carpophilus hemipterus (L.) were not significantly different from captures in traps baited with conspecific pheromones. Carpophilus davidsoni and C. mutilatus were cross-attracted to traps baited with the pheromone of the other species, but numbers were significantly reduced compared with traps baited with conspecific or heterospecific pheromones. Multispecies lures will improve prospects for the commercial use of synthetic aggregation pheromones in Carpophilus beetle management in stone-fruit orchards.