Understanding the role of clay silicate nanoparticles with organic modifiers in thermal curing of cyanate ester resin

The catalytic effect of montmorillonite clay nanoparticles containing organic modifiers such as quaternary phosphonium salts on cure mechanism of cyanate ester resin (RS-9D) was studied by differential scanning calorimetry (DSC) measurements, FT-IR and NMR spectroscopy as well as mass-spectrometry. The results show that the net catalytic effect arises from the presence of moisture associated with nanoclay particles where organic modifiers act as moisture transport agents. Possible mechanisms for cure pathways are discussed.     

Continuous silica coatings on glass fibers via bioinspired approaches

Simple methods for producing continuous inorganic coatings on fibers have application in multiple technologies. The application of bioinspired strategies for the formation of particulate inorganic materials has been widely investigated and provides routes to inorganic materials under environmentally benign conditions. In this work, we describe the formation of stable and continuous inorganic coatings on glass fibers via the polymerization of silica in the presence of biopolymers. The formation of both organic and inorganic coatings was investigated via X-ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray analysis. The simple route to silica coatings presented herein could be interesting for the development of functional hybrid fibrous materials suitable for catalytic and sensor applications, given the homogeneous nature of the silica films and the benign conditions employed for film formation.     

Use of contactless conductivity detection for non-invasive characterisation of monolithic stationary-phase coatings for application in capillary ion chromatography

A capacitively-coupled contactless conductivity detector (C4D) has been utilised as an on-capillary detector within a capillary ion chromatograph, incorporating a reversed-phase monolithic silica capillary column semi-permanently modified with a suitable ionic surfactant. The monolithic capillary column (150 x 0.1 mm i.d.) was modified using sodium dioctyl sulfosuccinate (DOSS), an anionic surfactant, for the separation of small inorganic and organic cations. With the use of the on-capillary conductivity detector, the longitudinal homogeneity and temporal stability of the coating were investigated. The approach allowed a detailed non-invasive observation of the nature of the ion-exchange coating over time, and an example of an application of the technique to produce a longitudinal stationary-phase charge gradient is shown. An investigation of the basis of the measured on-capillary conductivity was carried out with a counter ion study, clearly showing the on-capillary detection technique could also distinguish between chemical forms of the immobilised ion exchanger. The above method was used to produce a stable and homogeneously-modified monolithic ion-exchange capillary column, for application to the separation of inorganic alkaline earth cations and amino acids.     

Capillary ion chromatography of inorganic anions on octadecyl silica monolith modified with an amphoteric surfactant

A reversed-phase monolithic silica based capillary column (Onyx C(18), 150 mm x 0.1 mm) was modified with the amphoteric surfactant, N-dodecyl-N,N-(dimethylammonio)undecanoate (DDMAU) and evaluated for the separation and determination of inorganic anions using on-column capacitively coupled contactless conductivity detection (C(4)D). The chromatographic performance of the column was evaluated and under optimal conditions separation efficiencies of 56,200 plates per meter or 7025 plates per column (at detection point) were observed (for iodide). Direct plumbing of the capillary column to the micro-injector and on-column detection eliminated extra-column band broadening, thus allowing accurate analysis of van Deemter curves obtained for the monolithic capillary column. The calculated value for the C-term in the obtained van Deemter curve was between 3 and 4 ms for inorganic anions, allowing for the utilisation of relatively high flow rates without significant losses in efficiency. The performance of the C(4)D detector was investigated and compared for detection on an open tubular capillary column and on the modified monolithic silica capillary column. The on-column detection approach did not result in any significant decrease in peak sensitivity for the monolith compared to responses recorded for open tubular capillary columns, and in addition meant the system could be applied to rapid separations by simple variation in apparent column length. The proposed chromatographic system allowed for detection of common anions at sub-ppm level with a 10 nL injection volume. Additionally, on-column detection allowed visualisation of the development of the separation at any point in time and evaluation of the longitudinal uniformity of the ion-exchange coating.     

Benchmarking of electro-optic monitors for femtosecond electron bunches

The longitudinal profiles of ultrashort relativistic electron bunches at the soft x-ray free-electron laser FLASH have been investigated using two single-shot detection schemes: an electro-optic (EO) detector measuring the Coulomb field of the bunch and a radio-frequency structure transforming the charge distribution into a transverse streak. A comparison permits an absolute calibration of the EO technique. EO signals as short as 60 fs (rms) have been observed, which is a new record in the EO detection of single electron bunches and close to the limit given by the EO material properties.     

State-dependent doubly weighted stochastic simulation algorithm for automatic characterization of stochastic biochemical rare events

In recent years there has been substantial growth in the development of algorithms for characterizing rare events in stochastic biochemical systems. Two such algorithms, the state-dependent weighted stochastic simulation algorithm (swSSA) and the doubly weighted SSA (dwSSA) are extensions of the weighted SSA (wSSA) by H. Kuwahara and I. Mura [J. Chem. Phys. 129, 165101 (2008)]. The swSSA substantially reduces estimator variance by implementing system state-dependent importance sampling (IS) parameters, but lacks an automatic parameter identification strategy. In contrast, the dwSSA provides for the automatic determination of state-independent IS parameters, thus it is inefficient for systems whose states vary widely in time. We present a novel modification of the dwSSA--the state-dependent doubly weighted SSA (sdwSSA)--that combines the strengths of the swSSA and the dwSSA without inheriting their weaknesses. The sdwSSA automatically computes state-dependent IS parameters via the multilevel cross-entropy method. We apply the method to three examples: a reversible isomerization process, a yeast polarization model, and a lac operon model. Our results demonstrate that the sdwSSA offers substantial improvements over previous methods in terms of both accuracy and efficiency.     

Quantitative nanostructural and single-molecule force spectroscopy biomolecular analysis of human-saliva-derived exosomes

Exosomes are naturally occurring nanoparticles with unique structure, surface biochemistry, and mechanical characteristics. These distinct nanometer-sized bioparticles are secreted from the surfaces of oral epithelial cells into saliva and are of interest as oral-cancer biomarkers. We use high- resolution AFM to show single-vesicle quantitative differences between exosomes derived from normal and oral cancer patient's saliva. Compared to normal exosomes (circular, 67.4 ± 2.9 nm), our findings indicate that cancer exosome populations are significantly increased in saliva and display irregular morphologies, increased vesicle size (98.3 ± 4.6 nm), and higher intervesicular aggregation. At the single-vesicle level, cancer exosomes exhibit significantly (P < 0.05) increased CD63 surface densities. To our knowledge, it represents the first report detecting single-exosome surface protein variations. Additionally, high-resolution AFM imaging of cancer saliva samples revealed discrete multivesicular bodies with intraluminal exosomes enclosed. We discuss the use of quantitative, nanoscale ultrastructural and surface biomolecular analysis of saliva exosomes at single-vesicle- and single-protein-level sensitivities as a potentially new oral cancer diagnostic.     

Simple, robust control and synchronization of the Lorenz system

Simple and robust techniques based on time delay estimation (TDE) are proposed to control and synchronize the Lorenz system. TDE provides a simple and easily applicable control input that does not require a precise system model and cancels a wide class of uncertainties. Both the tracking error and estimation error converge in finite time. Control and synchronization are achieved with a single control architecture, even in the presence of parameter variation and disturbance. Simulation results demonstrate fast convergence to the desired states and robustness to uncertainties and TDE error.     

Atomistic examinations of the solid-phase epitaxial growth of silicon

The low-temperature vapor deposition of silicon thin films and the ion implantation of silicon can result in the formation of amorphous silicon layers on a crystalline silicon substrate. These amorphous layers can be crystallized by a thermally activated solid-phase epitaxial (SPE) growth process. The transformations are rapid and initiate at the buried amorphous to crystalline interface within the film. The initial stages of the transformation are investigated here using a molecular dynamics simulation approach based upon a recently proposed bond order potential for silicon. The method is used first to predict an amorphous structure for a rapidly cooled silicon melt. The radial distribution function of this structure is shown to be similar to that observed experimentally. Molecular dynamics simulations of its subsequent crystallization indicate that the early stage, rate limiting mechanism appears to be removal of tetrahedrally coordinated interstitial defects in the nominally crystalline region just behind the advancing amorphous to crystalline transition front. The activation barriers for this interstitials migration within the bulk crystal lattice are calculated and are found to be comparable to the activation energy of the overall solid-phase epitaxial growth process simulated here.     

On the finite element analysis of woven fabric impact using multiscale modeling techniques

Finite element modeling of the impact of flexible woven fabrics using a yarn level architecture allows the capturing of complex projectile-fabric and yarn–yarn level interactions, however it requires very large computational resources. This paper presents a multiscale modeling technique to simulate the impact of flexible woven fabrics. This technique involves modeling the fabric using a yarn level architecture around the impact region and a homogenized or membrane type architecture at far field regions. The level of modeling resolution decreases with distance away from the impact zone. This results in a finite element model with much lower computational requirements. The yarns are modeled using both solid and shell finite elements. Impedances are matched across all interfaces created between the various regions of the model to prevent artificial reflections of the longitudinal strain waves. A systematic approach is presented to determine geometric and material parameters of the homogenized zone. The multiscale model is extensively validated against baseline models. The limitations of using shell elements to model the yarn level architecture underneath the projectile are addressed.