Kalasin S.,20 Governors Drive |
Browne E.P.,40 Thatcher Road |
Arcaro K.F.,40 Thatcher Road |
Santore M.M.,20 Governors Drive
RSC Advances | Year: 2017
This work explored how molecularly non-specific polycationic nanoscale features on a collecting surface control kinetic and selectivity aspects of mammalian cell capture. Key principles for selective collector design were demonstrated by comparing the capture of two closely related breast cancer cell lines: MCF-7 and TMX2-28. TMX2-28 is a tamoxifen-selected clone of MCF-7. The collector was a silica surface, negatively-charged at pH 7.4, containing isolated molecules (∼8 nm diameter) of the cationic polymer, poly(dimethyl-aminoethylmethacrylate), pDMAEMA. Important in this work is the non-selective nature of the pDMAEMA interactions with cells: pDMAEMA generally adheres negatively charged particles and cells in solution. We show here that selectivity towards cells results from collector design: this includes competition between repulsive interactions involving the negative silica and attractions to the immobilized pDMAEMA molecules, the random pDMAEMA arrangement on the surface, and the concentration of positive charge in the vicinity of the adsorbed pDMAEMA chains. The latter act as nanoscopic cationic surface patches, each weakly attracted to negatively-charged cells. Collecting surfaces engineered with an appropriate amount pDMAEMA, exposed to mixtures of MCF-7 and TMX2-28 cells preferentially captured TMX2-28 with a selectivity of 2.5. (This means that the ratio of TMX2-28 to MCF cells on the surface was 2.5 times their compositional ratio in free solution.) The ionic strength-dependence of cell capture was shown to be similar to that of silica microparticles on the same surfaces. This suggests that the mechanism of selective cell capture involves nanoscopic differences in the contact areas of the cells with the collector, allowing discrimination of closely related cell line-based small scale features of the cell surface. This work demonstrated that even without molecular specificity, selectivity for physical cell attributes produces adhesive discrimination. © The Royal Society of Chemistry.
Selhorst R.C.,20 Governors Drive |
Puodziukynaite E.,20 Governors Drive |
Dewey J.A.,20 Governors Drive |
Wang P.,University of Massachusetts Amherst |
And 3 more authors.
Chemical Science | Year: 2016
Transition metal dichalcogenides (TMDCs) such as MoS2 comprise an important class of 2D semiconductors with numerous interesting electronic and mechanical features. Full utilization of TMDCs in materials and devices, however, necessitates robust functionalization methods. We report well-defined tetrathiafulvalene (TTF)-based polymers, exploiting synthetic routes that overcome challenges previously associated with these systems. These platforms enable basal plane coordinative interactions with MoS2, conceptually in parallel with pyrene-containing platforms for graphene and carbon nanotube modification. Not yet reported for TMDCs, these non-covalent interactions are universal and effective for MoS2 irrespective of the lattice structure, affording significantly enhanced solution stabilization of the nanosheets. Additionally, the TTF-functionalized polymers offer electronic structure modulation of MoS2 by ground state charge transfer and work function reduction, demonstrated using Kelvin probe force microscopy (KPFM). Notably, coordination and electronic effects are amplified for the TTF-polymers over TTF itself. Experiments are supported by first-principles density functional theory (DFT) calculations that probe polymer-TTF surface interactions with MoS2 and the resultant impact on electronic properties. © The Royal Society of Chemistry 2016.
Pham J.T.,20 Governors Drive |
Lawrence J.,20 Governors Drive |
Grason G.M.,20 Governors Drive |
Emrick T.,20 Governors Drive |
Crosby A.J.,20 Governors Drive
Physical Chemistry Chemical Physics | Year: 2014
Hybrid materials that possess high inorganic fractions of nanoscale particles can be advantageous for a wide range of functions, from optoelectronic or electronic devices to drug delivery. However, many current nanoparticle (NP) based materials lack the necessary combination of simple fabrication and robust mechanical properties that span across length scales greater than tens of microns. We have developed a facile, evaporative assembly method called flow coating to create NP based ribbons that can subsequently form helical structures. Here we analytically examine the stretching properties of these helical ribbons which are nanometers thick, microns wide, and arbitrarily long. We find that the force-extension behavior is well described by the elastic and surface energies, which can be used as a guideline for their design. In addition, we show that the properties may be tuned by changing the ribbon dimensions or material composition to yield a different stiffness. These macroscale mechanical properties, along with properties inherent to the nanometer length scale of the particles can provide tunable multifunctionality for a number of applications. This journal is © the Partner Organisations 2014.