Novel routes to new chiral rings and cages

The successful synthesis and characterisation of a series of new chiral cages was achieved through the use of a BINOL backbone linked to a variety of organotin carboxylates. These novel chiral cages may ultimately find use as catalysts in reaction syntheses for the pharmaceutical industry.

Controlling nanoparticle formation via sizable cages of supramolecular soft materials

We present a new generic strategy to fabricate nanoparticles in the “cages” within the fibrous networks of supramolecular soft materials. As the cages can be acquired by a design-and-production manner, the size of nanoparticles synthesized within the cages can be tuned accordingly. To implement this idea, both selenium and silver were chosen for the detailed investigation. It follows that the sizes of selenium and silver nanoparticles can be controlled by tuning the pore size of the fiber networks in the material. When the concentration of the gelator is high enough, monodisperse nanoparticles can be prepared. More interestingly, the morphology of the nanoparticles can be altered: silver disks can be formed when the concentrations of both the gelator and silver nitrate are sufficiently low. As the fiber network serves as a physical barrier and semisolid support for the nanoparticles, the stability in the aqueous media and the ease of application of these nanoparticles can be substantially enhanced. This robust surfactant-free approach will not only allow the controlled fabrication of nanoparticles, but also can be applied to the fabrication of composite materials for robust applications.

Stories from high school and prisons rattle institutional cages

AbstractThis paper is based on two research projects. One considered ‘unsettling’Aboriginal prisoner education and the other ‘troubling’ education in high school.Juxtaposed are two critical research methodologies; critical ethnography and arelational critical allied methodology. Whilst these may at first appear very similar,on closer scrutiny it becomes clearer that independently, the place of the researcherbecomes situated in a somewhat different relationship with participants. Inworking through these layers of difference, what emerges are the entwined voicesof participants who are clearly telling us what ‘bars hold them in their cages’ andwhat spaces between could be transformational.

Fused [n] polynorbornanes in coordination cages and preorganised hosts

 Dr. Johnstone’s research focussed on the design, synthesis and characterisation of molecular architectures based on the [n]polynorbornane framework. This work resulted in the development of novel supramolecular systems including coordination cages and molecular receptors for anions.

Modular synthesis of linear Bis- and Tris-monodentate fused [6]Polynorbornane-Based Ligands and their assembly into coordination cages

A modular approach has been developed for the synthesis of rigid linear di- and tritopic ligands based on a fused [6]polynorbornane scaffold. The design provides up to three sites for installing functionality, including both "ends" and a "central" position with the advantage that each region can be independently addressed during synthesis. To illustrate the utility of the approach, both pyridyl and picolyl units were incorporated to provide six new ligands, with centers and ends either matched or mismatched. Indeed, both [M2 L4 ] cages with endohedral functionality and [M3 L4 ] complexes were cleanly produced from these ligands with assembled structures confirmed by using (1) H NMR spectroscopy, HRMS, and molecular modelling.

A non-fullerene electron acceptor based on central carbazole and terminal diketopyrrolopyrrole functionalities for efficient, reproducible and solution-processable bulk-heterojunction devices

A novel, solution-processable non-fullerene electron acceptor, 6,6′-((9-(heptadecan-9-yl)-9H-carbazole-2,7-diyl)bis(thiophene-5,2-diyl))bis(2,5-bis(2-ethylhexyl)-3-(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (coded as N7), based on central carbazole and terminal diketopyrrolopyrrole building blocks was designed, synthesized and characterized. N7 displayed excellent solubility, thanks to its design allowing incorporation of numerous lipophilic chains, thermal stability, and afforded a 2.30% power conversion efficiency with a high open-circuit voltage (1.17 V) when tested with the conventional donor polymer poly(3-hexylthiophene) in solution-processable bulk-heterojunction devices. To our knowledge, not only is N7 the first reported chromophore based on carbazole and diketopyrrolopyrrole functionalities but the open-circuit voltage reported here is among the highest values for a single junction bulk-heterojunction device that has been fabricated using a simple device architecture, with reproducible outcomes and with no special treatment.

Naphthalene diimide-based non-fullerene acceptors for simple, efficient, and solution-processable bulk-heterojunction devices

Two solution processable, non-fullerene electron acceptors, 2,2′-(((2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-exahydrobenzo[lmn][3,8]phenanthroline-4,9-diyl)bis(thiophene-5,2-diyl))bis(methanylylidene))dimalononitrile (R1) and (2Z,2′Z)-3,3′-((2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydrobenzo[lmn][3,8]phenanthroline-4,9-diyl)bis(thiophene-5,2-diyl))bis(2-(4-nitrophenyl) acrylonitrile) (R2), comprised of central naphthalene diimide and two different terminal accepting functionalities, malononitrile and 2-(4-nitrophenyl)acetonitrile, respectively, were designed and synthesised. The central and terminal accepting functionalities were connected via a mild conjugated thiophene linker. Both of the new materials (R1 and R2) displayed high thermal stability and were found to have energy levels matching those of the archetypal electron donor poly(3-hexylthiophene). A simple, solution-processable bulk-heterojunction device afforded a promising power conversion efficiency of 2.24% when R2 was used as a non-fullerene electron acceptor along with the conventional donor polymer poly(3-hexylthiophene). To the best of our knowledge, the materials reported herein are the first examples in the literature where synchronous use of such accepting blocks is demonstrated for the design and development of efficient non-fullerene electron acceptors.

A four-directional non-fullerene acceptor based on tetraphenylethylene and diketopyrrolopyrrole functionalities for efficient photovoltaic devices with a high open-circuit voltage of 1.18 V

Through the conjunction of tetraphenylethylene and diketopyrrolopyrrole functionalities, a novel four-directional non-fullerene electron acceptor (denoted as 4D) was designed, synthesized and characterized. The new chromophore is highly soluble (for instance >30 mg mL(-1) in o-dichlorobenzene), thermally stable, and exhibits energy levels matching those of the conventional and routinely used donor polymer poly(3-hexyl thiophene). A power conversion efficiency of 3.86% was obtained in solution-processable bulk-heterojunction devices with a very high open circuit voltage of 1.18 V.

Growth rates of the infaunal bivalve Soletellina alba (Lamarck, 1818) (Bivalvia: Psammobiidae) in an intermittent estuary of southern Australia

Caging and a mark–recapture design were used to estimate the growth rate of the brittle, infaunal bivalve Soletellina alba in the Hopkins River estuary. The growth of both caged and uncaged individuals was monitored at three sites near the mouth of the estuary over 180 days. Growth rates did not differ for caged and uncaged bivalves, or for bivalves subject to different amounts of handling, or between sites. Growth did differ between consecutive time intervals, which was attributable to negligible growth occurring during the colder months of autumn/winter. Comparisons of the condition (as indicated by total mass for length³) of S. alba were inconsistent between sites for caged and uncaged bivalves and for those subject to different amounts of handling. Soletellina alba is a rapidly growing bivalve with mean growth rates for the three time intervals being 0.04±0.002 mm day⁻¹ in summer, 0.02±0.001 mm day⁻¹ in autumn and 0.03±0.001 mm day⁻¹ from summer to winter. Using existing literature, it was shown that a significant relationship exists between maximum shell length and onset of sexual maturity in bivalve molluscs. This relationship predicts that S. alba should reach the onset of sexual maturity at 15.8 mm length. Therefore, it appears that it may be possible for juvenile S. alba (<1 mm) to grow, reach sexual maturity and reproduce in between annual mass-mortality events caused by winter flooding.

Fisheries and cage culture of three reservoirs in west Java, Indonesia; a case study of ambitious development and resulting interactions

The interactions between cage culture and wild fishery activities in three Indonesian reservoirs, Saguling, Cirata and Jatiluhur, of the greater Ciratum watershed, West Java, were evaluated using historical data and interviews with cage culture operators. In all three reservoirs, cage culture of common carp, Cyprinus carpio L., and later of common carp and Nile tilapia, Oreochromis niloticus (L.), were encouraged as an alternative livelihood for persons displaced by the impoundment. Currently, a two-net culture system, locally known as 'lapis dua', in which in the inner cage (7 × 7 × 3 m) is used for common carp culture and the outer cage (7 × 7 × 5/7 m) is stocked with Nile tilapia, is practised. On average each cage is stocked with  approximately 100 kg fingerlings each of common carp and Nile tilapia. The numbers of cages and production of cultured fish has increased in the reservoirs, but total and per cage production began to decline from about 1995 in Saguling from 2200 kg cage−1 in 1989 to <500 kg cage−1 in 2002, and in Cirata from a peak of approximately 2300 kg cage−1 in 1995 to approximately 400 kg cage−1 in 2002. In Jatiluhur, which has a considerably lower cage density, total fish production and production per cage has increased since 2000, and currently is approximately 4000 kg cage−1, close to production in the early years of cage culture activities. The cage culture operations also resulted in substantial nutrient loading, estimated at 3.2, 15.2 and 3.1 t of nitrogen and 134, 636 and 128 kg of phosphorous per year in the maximum years of production for Saguling, Cirata and Jatiluhur reservoirs, respectively. In later years, when cage culture production was high, fish kills occurred in the cages, and in Jatiluhur reservoir coincided with a dramatic decline in wild fishery catches. An attempt is made to determine the maximum number of cages for each of the reservoirs that will bring long-term sustainability of cage culture operations and the wild fisheries in the three reservoirs.

Effect of cage colour and light environment on the skin colour of Australian Snapper Pagrus auratus (Bloch & Schneider, 1801)

A two-factor experiment was performed to evaluate the effects of cage colour (black or white 0.5 m³ experiment cages) and light environment (natural sunlight or reduced level of natural sunlight) on the skin colour of darkened Australian snapper. Each treatment was replicated four times and each replicate cage was stocked with five snapper (mean weight=351 g). Snapper exposed to natural sunlight were held in experimental cages located in outdoor tanks. An approximately 70% reduction in natural sunlight (measured as PAR) was established by holding snapper in experimental cages that were housed inside a 'shade-house' enclosure. The skin colour of anaesthetized fish was measured at stocking and after a 2-, 7- and 14-day exposure using a digital chroma-meter (Minolta CR-10) that quantified skin colour according to the L*a*b* colour space. At the conclusion of the experiment, fish were killed in salt water ice slurry and post-mortem skin colour was quantified after 0.75, 6 and 22 h respectively. In addition to these trials, an ad hoc market appraisal of chilled snapper (mean weight=409 g) that had been held in either white or in black cages was conducted at two local fish markets. Irrespective of the sampling time, skin lightness (L*) was significantly affected by cage colour (P<0.05), with fish in white cages having much higher L* values (L*≈64) than fish held in black cages (L*≈49). However, the value of L* was not significantly affected by the light environment or the interaction between cage colour and the light environment. In general, the L* values of anaesthetized snapper were sustained post mortem, but there were linear reductions in the a* (red) and b* (yellow) skin colour values of chilled snapper over time. According to the commercial buyers interviewed, chilled snapper that had been reared for a short period of time in white cages could demand a premium of 10–50% above the prices paid for similar-sized snapper reared in black cages. Our results demonstrate that short-term use of white cages can reduce the dark skin colour of farmed snapper, potentially improving the profitability of snapper farming.

Effect of carotenoids and background colour on the skin pigmentation of Australian snapper Pagrus auratus (Bloch & Schneider, 1801)

Three 2-factor experiments were conducted to determine the effects of background colour and synthetic carotenoids on the skin colour of Australian snapper Pagrus auratus. Initially, we evaluated the effects on skin colour of supplementing diets for 50 days with 60 mg kg⁻¹ of either astaxanthin (LP; Lucantin^®Pink), canthaxanthin (LR; Lucantin^® Red), apocarotenoic acid ethyl ester (LY; Lucantin^® Yellow), selected combinations of the above or no carotenoids and holding snapper (mean weight=88 g) in either white or black cages. In a second experiment, all snapper (mean weight=142 g) from Experiment 1 were transferred from black to white, or white to white cages to measure the short-term effects of cage colour on skin L*, a* and b* colour values. Skin colour was measured after 7 and 14 days, and total carotenoid concentrations were determined after 14 days.

Cage colour was the dominant factor affecting the skin lightness of snapper with fish from white cages much lighter than fish from black cages. Diets containing astaxanthin conferred greatest skin pigmentation and there were no differences in redness (a*) and yellowness (b*) values between snapper fed 30 or 60 mg astaxanthin kg⁻¹. Snapper fed astaxanthin in white cages displayed greater skin yellowness than those in black cages. Transferring snapper from black to white cages increased skin lightness but was not as effective as growing snapper in white cages for the entire duration. Snapper fed astaxanthin diets and transferred from black to white cages were less yellow than those transferred from white to white cages despite the improvement in skin lightness (L*), and the total carotenoid concentration of the skin of fish fed astaxanthin diets was lower in white cages. Diets containing canthaxanthin led to a low level of deposition in the skin while apocarotenoic acid ethyl ester did not alter total skin carotenoid content or skin colour values in snapper.

In a third experiment, we examined the effects of dietary astaxanthin (diets had 60 mg astaxanthin kg⁻¹ or no added carotenoids) and cage colour (black, white, red or blue) on skin colour of snapper (mean weight=88 g) after 50 days. Snapper fed the astaxanthin diet were more yellow when held in red or white cages compared with fish held in black or blue cages despite similar feed intake and growth. The skin lightness (L* values) was correlated with cage L* values, with the lightest fish obtained from white cages. The results of this study suggest that snapper should be fed 30 mg astaxanthin kg⁻¹ in white cages for 50 days to increase lightness and the red colouration prized in Australian markets.

Effects of cage netting colour and density on the skin pigmentation and stress response of Australian snapper Pagrus auratus (Bloch & Schneider, 1801)

The unnaturally dark pigmentation of cultured Australian snapper Pagrus auratus can be improved through dietary astaxanthin supplementation and by holding fish in tanks with a white background. The practical application of these  laboratory-based findings was examined with two experiments to establish if the advantages of transferring fish to light coloured tanks before harvest could be achieved on-farm using white cages and to determine the effects of fish density on skin colour. For the first experiment, snapper (mean TL=29.7 cm) were transferred from a commercial snapper sea cage to black or white netted cages and fed diets supplemented with unesterified astaxanthin (supplied as Lucantin^® Pink, BASF) at 0 or 39 mg kg⁻¹ for 42 days. Skin colour was measured using the CIE L* (black–white), a* (green–red), b* (blue–yellow) colour scale. Snapper held in white netting cages became significantly lighter (higher L* ) than snapper held in black cages; however, values were not as high as previous laboratory-based studies in which snapper were held in white plastic-lined cages. Snapper fed astaxanthin displayed significantly greater a*and b* values, and total carotenoid concentrations after 42 days. In addition, total carotenoids were higher in fish from black than white cages. The second experiment was designed to investigate whether density reduced the improvements in skin colour achieved by holding fish in white coloured cages and whether cage colour affected stress. Snapper (mean weight=435 g) were acclimated to black cages and fed 39 mg kg⁻¹ astaxanthin for 44 days before transferring to black or white plastic-lined cages at 14 (low), 29 (mid) or 45 (high) kg m⁻³ for 7 days after which time skin colour, plasma cortisol and plasma glucose concentrations were measured. Skin lightness (L* ) was greater in snapper transferred to white plastic-lined cages with the lightest coloured fish obtained from the lowest density after 7 days. Density had no effect on plasma cortisol or glucose levels after 7 days, although plasma cortisol was elevated in snapper from black cages. For improved skin colouration we recommend feeding unesterified astaxanthin at 39 mg kg⁻¹ for approximately 6 weeks and transferring snapper to white plastic-lined cages or similar at low densities for short periods before harvest rather than producing fish in white netting sea cages subject to biofouling.

Cage colour and post-harvest K+ concentration affect skin colour of Australian snapper Pagrus auratus (Bloch & Schneider, 1801)

In an attempt to improve post-harvest skin colour in cultured Australian snapper Pagrus auratus, a two-factor experiment was carried out to investigate the effects of a short-term change in cage colour before harvest, followed by immersion in K⁺-enriched solutions of different concentrations. Snapper supplemented with 39 mg unesterified astaxanthin kg⁻¹ for 50 days were transferred to black (for 1 day) or white cages (for 1 or 7 days) before euthanasia by immersing fish in seawater ice slurries supplemented with 0, 150, 300, 450 or 600 mmol L⁻¹ K⁺ for 1 h. Each treatment was replicated with five snapper (mean weight=838 g) held individually within 0.2 m³ cages. L*, a* and b* skin colour values of all fish were measured after removal from K⁺ solutions at 0, 3, 6, 12, 24 and 48 h. After immersion in K⁺ solutions, fish were stored on ice. Both cage colour and K⁺ concentration significantly affected post-harvest skin colour (P<0.05), and there was no interaction between these factors at any of the measurement times (P>0.05). Conditioning dark-coloured snapper in white surroundings for 1 day was sufficient to significantly improve skin lightness (L*) after death. Although there was no difference between skin lightness values for fish held for either 1 or 7 days in white cages at measurement times up to 12 h, fish held in white cages for 7 days had significantly higher L* values (i.e. they were lighter) after 24 and 48 h of storage on ice than those held only in white cages for 1 day. K⁺ treatment also affected (improved) skin lightness post harvest although not until 24 and 48 h after removal of fish from solutions. Before this time, K⁺ treatment had no effect on skin lightness. Snapper killed by seawater ice slurry darkened (lower L*) markedly during the first 3 h of storage in contrast with all K⁺ treatments that prevented darkening. After 24 and 48 h of storage on ice, fish exposed to 450 and 600 mmol L⁻¹ K⁺ were significantly lighter than fish from seawater ice slurries. In addition, skin redness (a*) and yellowness (b*) were strongly dependent on K⁺ concentration. The initial decline in response to K⁺ was overcome by a return of a* and b* values with time, most likely instigated by a redispersal of erythrosomes in skin erythrophores. Fish killed with 0 mmol L⁻¹ K⁺ maintained the highest a* and b* values after death, but were associated with darker (lower L*) skin colouration. It is concluded that a combination of conditioning snapper in white surroundings for 1 day before harvest, followed by immersion in seawater ice slurries supplemented with 300–450 mmol L⁻¹ K⁺ improves skin pigmentation after >24 h of storage on ice.