Accurate measurement of the molecular thickness of thin organic shells on small inorganic cores using dynamic light scattering

Dynamic light scattering (DLS) has become a primary nanoparticle characterization technique with applications from materials characterization to biological and environmental detection. With the expansion in DLS use from homogeneous spheres to more complicated nanostructures, comes a decrease in accuracy. Much research has been performed to develop different diffusion models that account for the vastly different structures but little attention has been given to the effect on the light scattering properties in relation to DLS. In this work, small (core size < 5 nm) core-shell nanoparticles were used as a case study to measure the capping thickness of a layer of dodecanethiol (DDT) on Au and ZnO nanoparticles by DLS. We find that the DDT shell has very little effect on the scattering properties of the inorganic core and hence can be ignored to a first approximation. However, this results in conventional DLS analysis overestimating the hydrodynamic size in the volume and number weighted distributions. By introducing a simple correction formula that more accurately yields hydrodynamic size distributions a more precise determination of the molecular shell thickness is obtained. With this correction, the measured thickness of the DDT shell was found to be 7.3 ± 0.3 Å, much less than the extended chain length of 16 Å. This organic layer thickness suggests that on small nanoparticles, the DDT monolayer adopts a compact disordered structure rather than an open ordered structure on both ZnO and Au nanoparticle surfaces. These observations are in agreement with published molecular dynamics results.

Binding of small mono- and oligomeric integrin ligands to membrane-embedded integrins monitored by surface plasmon-enhanced fluorescence spectroscopy

We recently developed a binding assay format by incorporating native transmembrane receptors into artificial phospholipid bilayers on biosensor devices for surface plasmon resonance spectroscopy. By extending the method to surface plasmon-enhanced fluorescence spectroscopy (SPFS), sensitive recording of the association of even very small ligands is enabled. Herewith, we monitored binding of synthetic mono- and oligomeric RGD-based peptides and peptidomimetics to integrins alphavbeta3 and alphavbeta5, after having confirmed correct orientation and functionality of membrane-embedded integrins. We evaluated integrin binding of RGD multimers linked together via aminohexanoic acid (Ahx) spacers and showed that the dimer revealed higher binding activity than the tetramer, followed by the RGD monomers. The peptidomimetic was also found to be highly active with a slightly higher selectivity toward alphavbeta3. The different compounds were also evaluated in in vitro cell adhesion tests for their capacity to interfere with alphavbeta3-mediated cell attachment to vitronectin. We hereby demonstrated that the different RGD monomers were similarly effective; the RGD dimer and tetramer showed comparable IC50 values, which were, however, significantly higher than those of the monomers. Best cell detachment from vitronectin was achieved by the peptidomimetic. The novel SPFS-binding assay platform proves to be a suitable, reliable, and sensitive method to monitor the binding capacity of small ligands to native transmembrane receptors, here demonstrated for integrins.

On cloud computing service considerations for the small and medium enterprises

The concept of cloud computing services is appealing to the small and medium enterprises (SMEs), with the opportunity to acquire modern information technology resources as a utility and avoid costly capital investments in technology resources. However, the adoption of the cloud computing services presents significant challenges to the SMEs. The SMEs need to determine a path to adopting the cloud computing services that would ensure their sustainable presence in the cloud computing environment. Information about approaches to adopting the cloud computing services by the SMEs is fragmented. Through an interpretive design, we suggest that the SMEs need to have a strategic and incremental intent, understand their organizational structure, understand the external factors, consider the human resource capacity, and understand the value expectations from the cloud computing services to forge a successful path to adopting the cloud computing services. These factors would contribute to a model of cloud services for SMEs.

Interstellar molecules : Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. . The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Potential interstellar molecules : Formation of neutral C6CO from C6CO- in the gas phase

Computations at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G* level of theory indicate that neutral C6CO is a stable species. The ground state of this neutral is the singlet cumulene oxide :C=C=C=C=C=C=C=O. The adiabatic electron affinity and dipole moment of singlet C6CO are 2.47 eV and 4.13 D, respectively, at this level of theory. The anion (C6CO)(-.) should be a possible precursor to this neutral. It has been formed by an unequivocal synthesis in the ion source of a mass spectrometer by the S(N)2(Si) reaction between (CH3)(3)Si-C=C-C=C-C=C-CO-CMe3 and F- to form C-=C-C=C-C=C-CO-CMe3 which loses Me3C in the source to form C6CO-.. Charge stripping of this anion by vertical Franck-Condon oxidation forms C6CO, characterised by the neutralisation-reionisation spectrum (-NR+) of C6CO-., which is stable during the timeframe of this experiment (10(-6) s), Copyright (C) 2000 John Wiley & Sons, Ltd.

Accessibility of pores in coal to methane and carbon dioxide

Fluid–solid interactions in natural and engineered porous solids underlie a variety of technological processes, including geological storage of anthropogenic greenhouse gases, enhanced coal bed methane recovery, membrane separation, and heterogeneous catalysis. The size, distribution and interconnectivity of pores, the chemical and physical properties of the solid and fluid phases collectively dictate how fluid molecules migrate into and through the micro- and meso-porous media, adsorb and ultimately react with the solid surfaces. Due to the high penetration power and relatively short wavelength of neutrons, smallangle neutron scattering (SANS) as well as ultra small-angle scattering (USANS) techniques are ideally suited for assessing the phase behavior of confined fluids under pressure as well as for evaluating the total porosity in engineered and natural porous systems including coal. Here we demonstrate that SANS and USANS can be also used for determining the fraction of the pore volume that is actually accessible to fluids as a function of pore sizes and study the fraction of inaccessible pores as a function of pore size in three coals from the Illinois Basin (USA) and Bowen Basin (Australia). Experiments were performed at CO2 and methane pressures up to 780 bar, including pressures corresponding to zero average contrast condition (ZAC), which is the pressure where no scattering from the accessible pores occurs. Scattering curves at the ZAC were compared with the scattering from same coals under vacuum and analysed using a newly developed approach that shows that the volume fraction of accessible pores in these coals varies between �90% in the macropore region to �30% in the mesopore region and the variation is distinctive for each of the examined coals. The developed methodology may be also applied for assessing the volume of accessible pores in other natural underground formations of interest for CO2 sequestration, such as saline aquifers as well as for estimating closed porosity in engineered porous solids of technological importance.

Two-scale computational modelling of unsaturated flow in soils exhibiting small scale heterogeneities

Unsaturated water flow in soil is commonly modelled using Richards’ equation, which requires the hydraulic properties of the soil (e.g., porosity, hydraulic conductivity, etc.) to be characterised. Naturally occurring soils, however, are heterogeneous in nature, that is, they are composed of a number of interwoven homogeneous soils each with their own set of hydraulic properties. When the length scale of these soil heterogeneities is small, numerical solution of Richards’ equation is computationally impractical due to the immense effort and refinement required to mesh the actual heterogeneous geometry. A classic way forward is to use a macroscopic model, where the heterogeneous medium is replaced with a fictitious homogeneous medium, which attempts to give the average flow behaviour at the macroscopic scale (i.e., at a scale much larger than the scale of the heterogeneities). Using the homogenisation theory, a macroscopic equation can be derived that takes the form of Richards’ equation with effective parameters. A disadvantage of the macroscopic approach, however, is that it fails in cases when the assumption of local equilibrium does not hold. This limitation has seen the introduction of two-scale models that include at each point in the macroscopic domain an additional flow equation at the scale of the heterogeneities (microscopic scale). This report outlines a well-known two-scale model and contributes to the literature a number of important advances in its numerical implementation. These include the use of an unstructured control volume finite element method and image-based meshing techniques, that allow for irregular micro-scale geometries to be treated, and the use of an exponential time integration scheme that permits both scales to be resolved simultaneously in a completely coupled manner. Numerical comparisons against a classical macroscopic model confirm that only the two-scale model correctly captures the important features of the flow for a range of parameter values.

Small angle X-ray scattering mapping and kinetics study of sub-critical CO2 sorption by two Australian coals

Time- and position-resolved synchrotron small angle X-ray scattering data were acquired from samples of two Australian coal seams: Bulli seam (Bulli 4, Ro=1.42%, Sydney Basin), which naturally contains CO2 and Baralaba seam (Ro=0.67%, Bowen Basin), a potential candidate for sequestering CO2. This experimental approach has provided unique, pore-size-specific insights into the kinetics of CO2 sorption in the micro- and small mesopores (diameter 5 to 175 Å) and the density of the sorbed CO2 at reservoir-like conditions of temperature and hydrostatic pressure. For both samples, at pressures above 5 bar, the density of CO2 confined in pores was found to be uniform, with no densification in near-wall regions. In the Bulli 4 sample, CO2 first flooded the slit pores between polyaromatic sheets. In the pore-size range analysed, the confined CO2 density was close to that of the free CO2. The kinetics data are too noisy for reliable quantitative analysis, but qualitatively indicate faster kinetics in mineral-matter-rich regions. In the Baralaba sample, CO2 preferentially invaded the smallest micropores and the confined CO2 density was up to five times that of the free CO2. Faster CO2 sorption kinetics was found to be correlated with higher mineral matter content but, the mineral-matter-rich regions had lower-density CO2 confined in their pores. Remarkably, the kinetics was pore-size dependent, being faster for smaller pores. These results suggest that injection into the permeable section of an interbedded coal-clastic sequence could provide a viable combination of reasonable injectivity and high sorption capacity.

Interstellar molecules. Conversion or C3O-. to C3O in the gas phase

Neutral C3O has been prepared by collision induced neutralisation of the precursor radical anion formed by the reaction C-=C-CO-OEt --> C3O-. +EtO. The similar neutralisaaion reionisation (-NR+) and charge reversal (CR) spectra of C3O-. indicate that the potential surfaces of C3O and C3O+. show favourable vertical Franck-Condon overlap, This suggests that the bond connectivities of anion, neutral and cation C3O are the same. Copyright (C) 1999 John Wiley & Sons, Ltd.

Bond dissociation energies of organic molecules

In this Account we have compiled a list of reliable bond energies that are based on a set of critically evaluated experiments. A brief description of the three most important experimental techniques for measuring bond energies is provided. We demonstrate how these experimental data can be applied to yield the heats of formation of organic radicals and the bond enthalpies of more than 100 representative organic molecules.

Conversion of neutral C2COC2 to C4CO. potential interstellar molecules

Both [C4CO]−· and [C2COC2]−· are formed in the ion source of a VG ZAB 2HF mass spectrometer by the respective processes HO− + Me3Si–CC–CC–CO–CMe3 → [C4CO]−· + Me3SiOH + Me3C·, and Me3Si–CC–CO–CC–SiMe3 + SF6 + e → [C2COC2]−· + 2Me3SiF + SF4. The second synthetic pathway involves a double desilylation reaction similar to that first reported by Squires. The two radical anion isomers produce different and characteristic charge reversal spectra upon collisional activation. In contrast, following collision induced charge stripping, both radical anions produce neutral C4CO as evidenced by the identical neutralisation reionisation (−NR+) spectra. The exclusive rearrangement of C213COC2 to C413CO indicates that 12C–O bond formation is not involved in the reaction. Ab initio calculations (at the RCCSD(T)/aug-cc-pVDZ//B3LYP/6-31G∗ level of theory) have been used to investigate the reaction coordinates on the potential surfaces for both singlet and triplet rearrangements of neutral C2COC2. Singlet C2COC2 is less stable than singlet C4CO by 78.8 kcal mol−1 and requires only 8.5 kcal mol−1 of additional energy to effect conversion to C4CO by a rearrangement sequence involving three C–C ring opening/cyclisation steps.

Regulating small things : genes, gametes and nanotechnology

Biotechnology and nanotechnology both intersect with other technologies in ways that open new possibilities for further technological progress. The potential for increased convergence between technological fields highlights the need for regulatory frameworks to be integrated, flexible and responsive. Within a federal legal system such as Australia’s, there is a need to ensure that we adopt a coordinated national approach to the crafting of regulatory solutions. In addition, there is a need for global cooperation in the development of international standards and regulatory harmonisation. Finally, this article considers the role that law plays in negotiating risk in relation to new technologies.

Surface dosimetry for very small X-ray beams

Introduction The dose to skin surface is an important factor for many radiotherapy treatment techniques. It is known that TPS predicted surface doses can be significantly different from actual ICRP skin doses as defined at 70 lm. A number of methods have been implemented for the accurate determination of surface dose including use of specific dosimeters such as TLDs and radiochromic film as well as Monte Carlo calculations. Stereotactic radiosurgery involves delivering very high doses per treatment fraction using small X-ray fields. To date, there has been limited data on surface doses for these very small field sizes. The purpose of this work is to evaluate surface doses by both measurements and Monte Carlo calculations for very small field sizes. Methods All measurements were performed on a Novalis Tx linear accelerator which has a 6 MV SRS X-ray beam mode which uses a specially thin flattening filter. Beam collimation was achieved by circular cones with apertures that gave field sizes ranging from 4 to 30 mm at the isocentre. The relative surface doses were measured using Gafchromic EBT3 film which has the active layer at a depth similar to the ICRP skin dose depth. Monte Carlo calculations were performed using the BEAMnrc/EGSnrc Monte Carlo codes (V4 r225). The specifications of the linear accelerator, including the collimator, were provided by the manufacturer. Optimisation of the incident X-ray beam was achieved by an iterative adjustment of the energy, spatial distribution and radial spread of the incident electron beam striking the target. The energy cutoff parameters were PCUT = 0.01 MeV and ECUT = 0.700 - MeV. Directional bremsstrahlung splitting was switched on for all BEAMnrc calculations. Relative surface doses were determined in a layer defined in a water phantom of the same thickness and depth as compared to the active later in the film. Results Measured surface doses using the EBT3 film varied between 13 and 16 % for the different cones with an uncertainty of 3 %. Monte Carlo calculated surface doses were in agreement to better than 2 % to the measured doses for all the treatment cones. Discussion and conclusions This work has shown the consistency of surface dose measurements using EBT3 film with Monte Carlo predicted values within the uncertainty of the measurements. As such, EBT3 film is recommended for in vivo surface dose measurements.