Self-assembly of a tetranuclear macrocyclic copper(II) complex

A dinuclear macrocyclic complex is synthesized via the one-pot reaction of dipotassium nitroacetate, formaldehyde and a linear tetraamine copper(II) complex; the X-ray crystal structure of the product reveals an association of two dinuclear complexes to form a novel tetracopper(II) species.

Self-assembly of a charge-neutral molecular square

Complexation of cadmium(II) by the ditopic (bis-tridentate) thiocarbazone ligand 1,5-bis(6-methyl-2-pyridylmethylene) thiocarbonohydrazide, H2L1, results in the self-assembly of a charge-neutral 2 x 2 molecular grid, [Cd-4(L-1)(4)], comprising four metals and four ligands in an interlocked cyclic array. The solid-state structure of this tetramer has been established by X-ray crystallography and in solution by H-1 NMR spectroscopy. The presence of lower molecular weight oligomers was identified by both NMR and ESI-MS.

Mechanical properties of interfacial films formed by lysozyme self-assembly at the air-water interface

We present the first characterization of the mechanical properties of lysozyme films formed by self-assembly at the air-water interface using the Cambridge interfacial tensiometer (CIT), an apparatus capable of subjecting protein films to a much higher level of extensional strain than traditional dilatational techniques. CIT analysis, which is insensitive to surface pressure, provides a direct measure of the extensional stress-strain behavior of an interfacial film without the need to assume a mechanical model (e.g., viscoelastic), and without requiring difficult-to-test assumptions regarding low-strain material linearity. This testing method has revealed that the bulk solution pH from which assembly of an interfacial lysozyme film occurs influences the mechanical properties of the film more significantly than is suggested by the observed differences in elastic moduli or surface pressure. We have also identified a previously undescribed pH dependency in the effect of solution ionic strength on the mechanical strength of the lysozyme films formed at the air-water interface. Increasing solution ionic strength was found to increase lysozyme film strength when assembly occurred at pH 7, but it caused a decrease in film strength at pH 11, close to the pI of lysozyme. This result is discussed in terms of the significant contribution made to protein film strength by both electrostatic interactions and the hydrophobic effect. Washout experiments to remove protein from the bulk phase have shown that a small percentage of the interfacially adsorbed lysozyme molecules are reversibly adsorbed. Finally, the washout tests have probed the role played by additional adsorption to the fresh interface formed by the application of a large strain to the lysozyme film and have suggested the movement of reversibly bound lysozyme molecules from a subinterfacial layer to the interface.

A novel route to the synthesis of mesoporous Titania with full anatase nanocrystalline domains

A porous, high surface area TiO2 with anatase or rutile crystalline domains is advantageous for high efficiency photonic devices. Here, we report a new route to the synthesis of mesoporous titania with full anatase crystalline domains. This route involves the preparation of anatase nanocrystalline seed suspensions as the titania precursor and a block copolymer surfactant, Pluronic P123 as the template for the hydrothermal self-assembly process. A large pore (7 - 8 nm) mesoporous titania with a high surface area of 106 - 150 m(2)/g after calcination at 400degreesC for 4 h in air is achieved. Increasing the hydrothermal temperature decreases the surface area and creates larger pores. Characteristics of the seed precursors as well as the resultant mesoporous titania powder were studied using XRD analysis, N-2-adsorption/desorption analysis, and TEM. We believe these materials will be especially useful for photoelectrochemical solar cell and photocatalysis applications.

Formation of mesostructured titania thin films using iospropoxide precursors

Mesostructured titania thin films were prepared by an evaporation-induced self-assembly process. The highly acidic sot precursors contained titanium(IV) tetraisopropoxide (TTIP) as a titanium source, a tri-block copolymer Pluronic P123 as a template, and acetylacetonate and HCl as hydrolysis inhibitors. Characteristics of the resultant titania thin films were studied using X-ray diffraction (XRD) analysis, N-2-adsorption/desorption analysis, and transmission electron microscopy (TEM). XRD and TEM investigations on the as-synthesised films revealed the appearance of cubic-like, pseudohexagonal, and lamellar mesophases; depending on the amount of water in the sols of film precursors. Template removal by a calcination process yields high surface area (320-360 m(2)/g) mesoporous materials with crystalline anatase frameworks. Water content also influences the degree of anatase crystallinity of the calcined films. Higher water content resulted in improved anatase crystallinity. These nanostructured materials are of interest for photocatalysts, pbotoelectrochemical solar cells and other photonic devices. (C) 2003 Elsevier B.V. All rights reserved.

The in-vitro bioactivity of mesoporous bioactive glasses

Ordered mesoporous bioactive glasses (MBGs) with different compositions were prepared by using nonionic block copolymer surfactants as structure-directing agents through an evaporation-induced self-assembly process. Their in-vitro bioactivities were studied in detail by electron microscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma (ICP) atomic emission spectroscopy. The ICP element analysis results were further calculated in terms of the total consumption of Ca and P, Delta[Ca]/Delta[P] ratios, and ionic activity product (IP) of hydroxyapatite. Through the above analysis, it is clear that MBGs show a different structure-bioactivity correlation compared to conventional sol-gel-derivcd BGs. The in vitro bioactivity of MBGs is dependent on the Si/Ca ratio in the network when the other material parameters such as the mesostructure and texture properties (pore size, pore volume) are controlled. MBG 80S15C with relatively lower calcium content exhibits the best in vitro bioactivity, in contrast to conventional sol-gel-derived BGs where usually higher calcium percentage BGs (e.g. 60S35C) show better bioactivity. Calcination temperature is another important factor that influences the in vitro bioactivity. According to our results, MBGs calcined at 973 K may possess the best in vitro bioactivity. The influences of the composition and calcination temperature upon bioactivity are explained in terms of the unique structures of MBGs. (c) 2006 Elsevier Ltd. All rights reserved.

Assembly of Human Papillomavirus Type-16 Virus-Like Particles: Multifactorial Study of Assembly and Competing Aggregation

Pentameric capsomeres of human papillomavirus capsid protein L1 expressed in Escherichia coli self-assemble into virus-like particles (VLPs) in vitro. A multifactorial experimental design was used to explore a wide range of solution conditions to optimize the assembly process. The degree of assembly was measured using an enzyme-linked immunosorbent assay, and a high-throughput turbidity assay was developed to monitor competing aggregation. The presence of zinc ions in the assembly buffer greatly increased the incidence of aggregation and had to be excluded from the experiment for meaningful analysis. Assembly of VLPs was optimal at a pH of about 6.5, calcium and sodium ions had no measurable effect, and dithiothreitol and glutathione inhibited assembly. Tryptophan fluorescence spectroscopy demonstrated that an increase in urea concentration reduced the rate of VLP formation but had no effect on the final concentration of assembled VLPs. This study demonstrates the use of the hanging-drop vapor-diffusion crystallization method to screen for conditions that promote aggregation and the use of tryptophan fluorescence spectroscopy for real-time monitoring of the assembly process.

Structural development of silicated films self-assembled at the air-water interface

The development of structure perpendicular to and in the plane of the interface has been studied for mesoporous silicate films self-assembled at the air/water interface. The use of constrained X-ray and neutron specular reflectometry has enabled a detailed study of the structural development perpendicular to the interface during the pre-growth phase. Off-specular neutron reflectometry and grazing incidence X-ray diffraction has enabled the in-plane structure to be probed with excellent time resolution. The growth mechanism under the surfactant to silicate source ratios used in this work is clearly due to the self-assembly of micellar and molecular species at the air/liquid interface, resulting in the formation of a planar mesoporous film that is tens of microns thick. (C) 2003 Elsevier Science B.V. All rights reserved.

Extra-curricular involvement and self-regulation in children

The research investigated the relationship between extra-curricular involvement (ECI) and self-regulated behaviours in 8 to 9 year old children, and identified sex, location, and socio-economic status (SES) differences in their ECI and self-regulatory behaviours. 550 children from 44 schools in Queensland and New South Wales completed the Child Self-Regulatory Process Inventory and questions about their ECI. Nearly 90 percent of students were involved in at least one extra-curricular activity with the mean number of activities being 1.27. Girls and urban children were significantly more involved in school-based extra- curricular activities than their male and rural counterparts; there were no significant differences among SES groups. Urban children and children in the high SES group reported significantly greater involvement for non-school based activities. For the three self- regulation strategies, girls scored significantly higher than boys. Moreover, children in the high ECI group reported significantly greater use of self-regulation strategies than children in both the low and medium ECI groups. Implications of findings are discussed in light of the need for quality extra-curricular programs, especially in terms of emotional climate and self-directed activities.

Towards the preparative and large-scale precision manafacture of virus-like particles

Virus-like particles (VLPs) are of interest in vaccination, gene therapy and drug delivery, but their potential has yet to be fully realized. This is because existing laboratory processes, when scaled, do not easily give a compositionally and architecturally consistent product. Research suggests that new process routes might ultimately be based on chemical processing by self-assembly, involving the precision manufacture of precursor capsomeres followed by in vitro VLP self-assembly and scale-up to required levels. A synergistic interaction of biomolecular design and bioprocess engineering (i.e. biomolecular engineering) is required if these alternative process routes and, thus, the promise of new VLP products, are to be realized.

Biomolecular engineering at interfaces

A broad review of technologically focused work concerning biomolecules at interfaces is presented. The emphasis is on developments in interfacial biomolecular engineering that may have a practical impact in bioanalysis, tissue engineering, emulsion processing or bioseparations. We also review methods for fabrication in an attempt to draw out those approaches that may be useful for product manufacture, and briefly review methods for analysing the resulting interfacial nanostructures. From this review we conclude that the generation of knowledge and-innovation at the nanoscale far exceeds our ability to translate this innovation into practical outcomes addressing a market need, and that significant technological challenges exist. A particular challenge in this translation is to understand how the structural properties of biomolecules control the assembled architecture, which in turn defines product performance, and how this relationship is affected by the chosen manufacturing route. This structure-architecture-process-performance (SAPP) interaction problem is the familiar laboratory scale-up challenge in disguise. A further challenge will be to interpret biomolecular self- and directed-assembly reactions using tools of chemical reaction engineering, enabling rigorous manufacturing optimization of self-assembly laboratory techniques. We conclude that many of the technological problems facing this field are addressable using tools of modem chemical and biomolecular engineering, in conjunction with knowledge and skills from the underpinning sciences. (c) 2005 Elsevier Ltd. All rights reserved.

Molecular dynamics simulations of the hydrophobin SC3 at a hydrophobic/hydrophilic interface

Hydrophobins are small (similar to 100 aa) proteins that have an important role in the growth and development of mycelial fungi. They are surface active and, after secretion by the fungi, self-assemble into amphipathic membranes at hydrophobic/hydrophilic interfaces, reversing the hydrophobicity of the surface. In this study, molecular dynamics simulation techniques have been used to model the process by which a specific class I hydrophobin, SC3, binds to a range of hydrophobic/ hydrophilic interfaces. The structure of SC3 used in this investigation was modeled based on the crystal structure of the class II hydrophobin HFBII using the assumption that the disulfide pairings of the eight conserved cysteine residues are maintained. The proposed model for SC3 in aqueous solution is compact and globular containing primarily P-strand and coil structures. The behavior of this model of SC3 was investigated at an air/water, an oil/water, and a hydrophobic solid/water interface. It was found that SC3 preferentially binds to the interfaces via the loop region between the third and fourth cysteine residues and that binding is associated with an increase in a-helix formation in qualitative agreement with experiment. Based on a combination of the available experiment data and the current simulation studies, we propose a possible model for SC3 self-assembly on a hydrophobic solid/water interface.

Supra-assembly of siliceous vesicles

We report a new approach to produce macroporous (110 nm in diameter) ordered siliceous foams (MOSF) by using block copolymers as templates in the absence of any organic cosolvent. The fine three-dimensional honeycomb structure of MOSF was determined by electron tomography. A formation mechanism of MOSF that spans from the atomic to macroscopic scale is proposed, which involves the cooperative self-assembly of unilamellar vesicles followed by the supra-assembly of vesicles. The fusion of soft vesicles finally leads to MOSF with well-ordered and defined honeycomb structures.

Anatomy of a heating and assessment of critical self-heating parameters

Numerical modelling is a valuable tool for simulating the fundamental processes that take place during a heating. The models presented in this paper have enabled a quantitative assessment of the effects of initial pile temperature, pile size and mass and coal particle size on the development of a heating. All of these parameters have a certain criticality in the coal self-heating process.

The influence of the atmosphere on the sintering of aluminum

Alloys of Al, Al-0.15Mg, and Al-12Sn made using air atomized aluminum powder and pressed to green densities of 75 to 98 pet were sintered under argon or nitrogen. Sintering in argon is only effective at high green densities when magnesium is present. In contrast, highly porous aluminum can be sintered in nitrogen without the need for magnesium. The oxygen concentration in the gas is reduced by the aluminum through a self-gettering process. The outer layers of the porous powder compact serve as a getter for the inner layers such that the oxygen partial pressure is reduced deep within the pore network. Aluminum nitride then forms, either by direct reaction with the metal or by reduction of the oxide layer, and sintering follows.