Henry Bock

The differences in surfactant adsorption on carbon nanotubes and their bundles.

Dissipative particle dynamics simulations of a mesoscale model are performed to investigate the concentration dependence of surfactant adsorption on small-diameter carbon nanotubes and their bundles. Adsorption is found to follow fundamentally different mechanisms in the two cases because of the heterogeneity of the bundle surface and the difference in diameter of bundles compared to that of individual tubes. Whereas aggregation dominates adsorption on individual tubes, on bundles it is largely a Langmuir-type process. High adsorption energy sites on the outer surface of bundles, where surfactant molecules can interact with two tubes simultaneously, dominate at low coverage. They also cause adsorption on bundles to become significant well before adsorption on individual tubes starts. The difference in the adsorption mechanisms leads to a crossover point at higher concentrations, where the adsorbed amount per surface area on individual tubes becomes larger than that for the bundles.

Elasticity of human embryonic stem cells as determined by atomic force microscopy

The expansive growth and differentiation potential of human embryonic stem cells (hESCs) make them a promising source of cells for regenerative medicine. However, this promise is off set by the propensity for spontaneous or uncontrolled differentiation to result in heterogeneous cell populations. Cell elasticity has recently been shown to characterize particular cell phenotypes, with undifferentiated and differentiated cells sometimes showing significant differences in their elasticities. In this study, we determined the Youngs modulus of hESCs by atomic force microscopy using a pyramidal tip. Using this method we are able to take point measurements of elasticity at multiple locations on a single cell, allowing local variations due to cell structure to be identified. We found considerable differences in the elasticity of the analyzed hESCs, reflected by a broad range of Youngs modulus (0.05-10 kPa). This surprisingly high variation suggests that elasticity could serve as the basis of a simple and efficient large scale purification/separation technique to discriminate subpopulations of hESCs.

Surfactant-Induced Forces between Carbon Nanotubes

Dissipative particle dynamics simulations are employed to study surfactant-mediated forces between a pair of perpendicular carbon nanotubes (CNTs) coated by surfactants which form spherical micelles in bulk solution and on the tubes. Two force regimes are observed: at small tube/tube distances the force is attractive, whereas it is repulsive at larger distances. The attractive regime is dominated by a central micelle binding the tubes, while in the repulsive regime the contact region is depleted. The two regimes are separated by a discontinuous transition. The repulsive regime is critical for stabilizing CNT suspensions. Viewing rebundling as a thermally activated process, a connection between the repulsive force and the rebundling rate is established. We find that a larger hydrophilic surfactant headgroup creates a stronger and longer ranged tube/tube force, which reduces the rebundling rate significantly. The longer range originates directly from the further reaching head corona of the adsorbed surfactant layer. The larger magnitude of the force appears to be related to the axial compression force the adsorbed phase can sustain. This compression force appears to be the most critical factor for suspension design.

Structural Forces from Directed Self-Assembly†

We investigate a candidate structure for the bottom-up design of nanocomposite materials. At a pair of crossing carbon nanotubes, surfactants self-assemble into a micelle-like aggregate incorporating the two tubes. The aggregate forms as long as the gap between the tubes is smaller than the core diameter of a bulk micelle. Moreover, the absorbed surfactant aggregate generates an effective force between the tubes. The dependence of this force on the distance between the tubes is complex and includes structural components, such as layering, and a large attractive region at larger distances. This attraction appears to be entropic in nature and to originate from confinement of the surfactant head groups.

Angular Dependence of Surfactant-Mediated Forces Between Carbon Nanotubes

We employ dissipative particle dynamics to examine surfactant-mediated forces between two carbon nanotubes. Calculations are performed varying both the distance and the angle between the nanotubes. For small distances, a repulsive region is observed, followed by an overall attractive interval with strong oscillations in the force. Decreasing the angle between the tubes leads to a steady increase in the force, but the relative dependence on the separation distance is preserved. We find that the force scales linearly with the size of the overlap area between the tubes. This allows us to express the angle dependence by a simple equation, whereas the distance dependence is represented by a master curve. For the parallel case, the behavior is significantly different.

A scalable label-free approach to separate human pluripotent cells from differentiated derivatives

The broad capacity of pluripotent human embryonic stem cells (hESC) to grow and differentiate demands the development of rapid, scalable, and label-free methods to separate living cell populations for clinical and industrial applications. Here, we identify differences in cell stiffness, expressed as cell elastic modulus (CEM), for hESC versus mesenchymal progenitors, osteoblast-like derivatives, and fibroblasts using atomic force microscopy and data processing algorithms to characterize the stiffness of cell populations. Undifferentiated hESC exhibited a range of CEMs whose median was nearly three-fold lower than those of differentiated cells, information we exploited to develop a label-free separation device based on the principles of tangential flow filtration. To test the devices utility, we segregated hESC mixed with fibroblasts and hESC-mesenchymal progenitors induced to undergo osteogenic differentiation. The device permitted a throughput of 10(6)-10(7) cells per min and up to 50% removal of specific cell types per single pass. The level of enrichment and depletion of soft, pluripotent hESC in the respective channels was found to rise with increasing stiffness of the differentiating cells, suggesting CEM can serve as a major discriminator. Our results demonstrate the principle of a scalable, label-free, solution for separation of heterogeneous cell populations deriving from human pluripotent stem cells.

High-throughput assessment of mechanical properties of stem cell derived red blood cells, toward cellular downstream processing

Stem cell products, including manufactured red blood cells, require efficient sorting and purification methods to remove components potentially harmful for clinical application. However, standard approaches for cellular downstream processing rely on the use of specific and expensive labels (e.g. FACS or MACS). Techniques relying on inherent mechanical and physical properties of cells offer high-throughput scalable alternatives but knowledge of the mechanical phenotype is required. Here, we characterized for the first time deformability and size changes in CD34+ cells, and expelled nuclei, during their differentiation process into red blood cells at days 11, 14, 18 and 21, using Real-Time Deformability Cytometry (RT-DC) and Atomic Force Microscopy (AFM). We found significant differences (p < 0.0001; standardised mixed model) between the deformability of nucleated and enucleated cells, while they remain within the same size range. Expelled nuclei are smaller thus could be removed by size-based separation. An average Young’s elastic modulus was measured for nucleated cells, enucleated cells and nuclei (day 14) of 1.04 ± 0.47 kPa, 0.53 ± 0.12 kPa and 7.06 ± 4.07 kPa respectively. Our identification and quantification of significant differences (p < 0.0001; ANOVA) in CD34+ cells mechanical properties throughout the differentiation process could enable development of new routes for purification of manufactured red blood cells.

Unmodified multi-wall carbon nanotubes in polylactic acid for electrically conductive injection-moulded composites:

Tailoring the properties of natural polymers such as electrical conductivity is vital to widen the range of future applications. In this article, the potential of electrically conducting multi-wall carbon nanotube (MWCNT)/polylactic acid (PLA) composites produced by industrially viable melt mixing is assessed simultaneously to MWCNT influence on the composite’s mechanical strength and polymer crystallinity. Atomic force microscopy observations showed that melt mixing achieved an effective distribution and individualization of unmodified nanotubes within the polymer matrix. However, as a trade-off of the poor tube/matrix adhesion, the tensile strength was lowered. With 10 wt% MWCNT loading, the tensile strength was 26% lower than for neat PLA. Differential scanning calorimetric measurements indicated that polymer crystallization after injection moulding was nearly unaffected by the presence of nanotubes and remained at 15%. The resulting composites became conductive below 5 wt% loading and reached conductivities of 51 S m−1 at 10 wt%, which is comparable with conductivities reported for similar nanocomposites obtained at lab scale.

From aggregative adsorption to surface depletion: aqueous systems of CnEm amphiphiles at hydrophilic surfaces

ABSTRACT Adsorption of a short-chain nonionic amphiphile (C6E3) at the surface of mesoporous silica glass (CPG) was studied by a combination of adsorption measurements and mesoscale simulations. Adsorption measurements covering a wide composition range of the C6E3 + water system show that no adsorption occurs up to the critical micelle concentration, at which a sharp increase of adsorption is observed that is attributed to ad-micelle formation at the pore walls. Intriguingly, as the concentration is increased further, the surface excess of the amphiphile begins to decrease and eventually becomes negative, which corresponds to preferential adsorption of water rather than amphiphile at high amphiphile concentrations. The existence of such a surface-azeotropic point has not previously been reported in the surfactant adsorption field. Dissipative particle dynamics simulations were performed to reveal the structural origin of this transition from aggregative adsorption to surface depletion. The simulations indicate that this transition can be attributed to the repulsive interaction between head groups, causing depletion of the amphiphile in the region around the corona of the surface micelles.

Engineering self-assembly

Self-assembly can be loosely defined as the emergence of order in an initially disordered system by virtue of intrinsic interactions between the different components of the system, as opposed to being induced by external action. It is a phenomenon that is ubiquitous in the natural world and crucial in a myriad of practical applications. Some of the best known examples in nature are the formation of cell membranes, hierarchical DNA or protein assemblies, and the porous skeletons of invertebrate species like diatoms and sponges. Giant trees, that grow to 100 m in height, demonstrate impressively that self-assembly is not confined to small scales. Industrial applications range from the traditional uses of amphiphilic surfactants in detergency to the synthesis of porous, functional, and stimuli responsive nanomaterials. This diversity of existing applications and the prospect of many new ones have rendered self-assembly a rather wide-ranging research topic. The key challenge lies in the complexity of the systems, which makes discovery and understanding of the underlying assembly mechanisms very difficult for both experimentalists and theoreticians. The last few decades have seen a progressive shift in self-assembly research from a mainly experimental field to one in which theory and simulation play a key role. This arose from the realisation that only through detailed understanding of the molecular-level mechanisms of self-assembly can one hope to design and control such systems in practical applications. It is the contribution of molecular simulation to the goal of engineering self-assembling systems that is the focus of this special issue.