Characterizing the mechanics of cultured cell monolayers.

One-cell-thick monolayers are the simplest tissues in multicellular organisms, yet they fulfill critical roles in development and normal physiology. In early development, embryonic morphogenesis results largely from monolayer rearrangement and deformation due to internally generated forces. Later, monolayers act as physical barriers separating the internal environment from the exterior and must withstand externally applied forces. Though resisting and generating mechanical forces is an essential part of monolayer function, simple experimental methods to characterize monolayer mechanical properties are lacking. Here, we describe a system for tensile testing of freely suspended cultured monolayers that enables the examination of their mechanical behavior at multi-, uni-, and subcellular scales. Using this system, we provide measurements of monolayer elasticity and show that this is two orders of magnitude larger than the elasticity of their isolated cellular components. Monolayers could withstand more than a doubling in length before failing through rupture of intercellular junctions. Measurement of stress at fracture enabled a first estimation of the average force needed to separate cells within truly mature monolayers, approximately ninefold larger than measured in pairs of isolated cells. As in single cells, monolayer mechanical properties were strongly dependent on the integrity of the actin cytoskeleton, myosin, and intercellular adhesions interfacing adjacent cells. High magnification imaging revealed that keratin filaments became progressively stretched during extension, suggesting they participate in monolayer mechanics. This multiscale study of monolayer response to deformation enabled by our device provides the first quantitative investigation of the link between monolayer biology and mechanics.

Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

The parameter space of graphene chemical vapor deposition on polycrystalline Cu

A systematic study of the parameter space of graphene chemical vapor deposition (CVD) on polycrystalline Cu foils is presented, aiming at a more fundamental process rationale in particular regarding the choice of carbon precursor and mitigation of Cu sublimation. CH 4 as precursor requires H 2 dilution and temperatures ≥1000 °C to keep the Cu surface reduced and yield a high-quality, complete monolayer graphene coverage. The H 2 atmosphere etches as-grown graphene; hence, maintaining a balanced CH 4/H 2 ratio is critical. Such balance is more easily achieved at low-pressure conditions, at which however Cu sublimation reaches deleterious levels. In contrast, C 6H 6 as precursor requires no reactive diluent and consistently gives similar graphene quality at 100-150 °C lower temperatures. The lower process temperature and more robust processing conditions allow the problem of Cu sublimation to be effectively addressed. Graphene formation is not inherently self-limited to a monolayer for any of the precursors. Rather, the higher the supplied carbon chemical potential, the higher the likelihood of film inhomogeneity and primary and secondary multilayer graphene nucleation. For the latter, domain boundaries of the inherently polycrystalline CVD graphene offer pathways for a continued carbon supply to the catalyst. Graphene formation is significantly affected by the Cu crystallography; i.e., the evolution of microstructure and texture of the catalyst template form an integral part of the CVD process. © 2012 American Chemical Society.

A comprehensive study of lysozyme adsorption using dual polarization interferometry and quartz crystal microbalance with dissipation.

Protein adsorption plays a crucial role in biomaterial surface science as it is directly linked to the biocompatibility of artificial biomaterial devices. Here, elucidation of protein adsorption mechanism is effected using dual polarization interferometry and a quartz crystal microbalance to characterize lysozyme layer properties on a silica surface at different coverage values. Lysozyme is observed to adsorb from sparse monolayer to multilayer coverage. At low coverage an irreversibly adsorbed layer is formed with slight deformation consistent with side-on orientation. At higher coverage values dynamic re-orientation effects are observed which lead to monolayer surface coverages of 2-3 ng/mm² corresponding to edge-on or/and end-on orientations. These monolayer thickness values ranged between 3 and 4.5 nm with a protein density value of 0.60 g/mL and with 50 wt% solvent mass. Further increase of coverage results formation of a multilayer structure. Using the hydration content and other physical layer properties a tentative model lysozyme adsorption is proposed.

A comprehensive study of lysozyme adsorption using dual polarization interferometry and quartz crystal microbalance with dissipation

Protein adsorption plays a crucial role in biomaterial surface science as it is directly linked to the biocompatibility of artificial biomaterial devices. Here, elucidation of protein adsorption mechanism is effected using dual polarization interferometry and a quartz crystal microbalance to characterize lysozyme layer properties on a silica surface at different coverage values. Lysozyme is observed to adsorb from sparse monolayer to multilayer coverage. At low coverage an irreversibly adsorbed layer is formed with slight deformation consistent with side-on orientation. At higher coverage values dynamic re-orientation effects are observed which lead to monolayer surface coverages of 2-3 ng/mm2 corresponding to edge-on or/and end-on orientations. These monolayer thickness values ranged between 3 and 4.5 nm with a protein density value of 0.60 g/mL and with 50 wt% solvent mass. Further increase of coverage results formation of a multilayer structure. Using the hydration content and other physical layer properties a tentative model lysozyme adsorption is proposed. © 2012 Elsevier Ltd.

Polymer gate dielectrics with self-assembled monolayers for high-mobility organic thin-film transistors based on copper phthalocyanine

Organic thin-film transistors based on polycrystalline copper phthalocyanine (CuPc) were fabricated by using poly(vinyl alcohol) as gate dielectric. After treatment of the gate dielectric using an octadecyltrichlorosilane self-assembled monolayer, a mobility of up to 0.11 cm2/V∈s was achieved, which is comparable to that of single-crystal CuPc devices (0.1-1 cm2/V∈s). The surface morphology was analyzed and the possible reasons for the enhanced mobility are discussed. © 2009 Springer-Verlag.

Near-field characterization of chemical vapor deposition graphene in the microwave regime

Near-field measurements were performed at X-band frequencies for graphene on copper microstrip transmission lines. An improvement in radiation of 0.88 dB at 10.2 GHz is exhibited from the monolayer graphene antenna which has dc sheet resistivity of 985 Ω/sq. Emission characteristics were validated via ab initio simulations and compared to empirical findings of geometrically comparable copper patches. This study contributes to the current knowledge of the electronic properties of graphene. © 2013 AIP Publishing LLC.

Introducing carbon diffusion barriers for uniform, high-quality graphene growth from solid sources.

Carbon diffusion barriers are introduced as a general and simple method to prevent premature carbon dissolution and thereby to significantly improve graphene formation from the catalytic transformation of solid carbon sources. A thin Al2O3 barrier inserted into an amorphous-C/Ni bilayer stack is demonstrated to enable growth of uniform monolayer graphene at 600 °C with domain sizes exceeding 50 μm, and an average Raman D/G ratio of <0.07. A detailed growth rationale is established via in situ measurements, relevant to solid-state growth of a wide range of layered materials, as well as layer-by-layer control in these systems.

Intrinsic terahertz plasmon signatures in chemical vapour deposited graphene

Plasmonic resonance at terahertz (THz) frequencies can be achieved by gating graphene grown via chemical vapour deposition (CVD) to a high carrier concentration. THz time domain spectroscopy of such gated monolayer graphene shows resonance features around 1.6 THz, which appear as absorption peaks when the graphene is electrostatically p-doped and change to enhanced transmission when the graphene is n-doped. Superimposed on the Drude-like frequency response of graphene, these resonance features are related to the inherent poly-crystallinity of CVD graphene. An understanding of these features is necessary for the development of future THz optical elements based on CVD graphene. © 2013 AIP Publishing LLC.

All-chemical vapor deposited graphene/silicon nitride TFTs

All-chemical vapor deposited silicon nitride / monolayer graphene TFTs have been fabricated. Polychromatic Raman spectroscopy shows high quality monolayer graphene channels with uniform coverage and significant interfacial doping at the source-drain contacts. Nominal mobilities of approximately 1900 cm 2V-1s-1 have been measured opening up a potentially useful platform for analogue and RFR-based applications fabricated through allchemical vapor deposition processes. © The Electrochemical Society.

Generating suspended cell monolayers for mechanobiological studies.

Cell monolayers line most of the surfaces and cavities in the human body. During development and normal physiology, monolayers sustain, detect and generate mechanical stresses, yet little is known about their mechanical properties. We describe a cell culture and mechanical testing protocol for generating freely suspended cell monolayers and examining their mechanical and biological response to uniaxial stretch. Cells are cultured on temporary collagen scaffolds polymerized between two parallel glass capillaries. Once cells form a monolayer covering the collagen and the capillaries, the scaffold is removed with collagenase, leaving the monolayer suspended between the test rods. The suspended monolayers are subjected to stretching by prying the capillaries apart with a micromanipulator. The applied force can be measured for the characterization of monolayer mechanics. Monolayers can be imaged with standard optical microscopy to examine changes in cell morphology and subcellular organization concomitant with stretch. The entire preparation and testing protocol requires 3-4 d.

Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H 25NH3)2PbI4(1-y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices. © 2013 AIP Publishing LLC.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Nonautonomous contact guidance signaling during collective cell migration.

Directed migration of groups of cells is a critical aspect of tissue morphogenesis that ensures proper tissue organization and, consequently, function. Cells moving in groups, unlike single cells, must coordinate their migratory behavior to maintain tissue integrity. During directed migration, cells are guided by a combination of mechanical and chemical cues presented by neighboring cells and the surrounding extracellular matrix. One important class of signals that guide cell migration includes topographic cues. Although the contact guidance response of individual cells to topographic cues has been extensively characterized, little is known about the response of groups of cells to topographic cues, the impact of such cues on cell-cell coordination within groups, and the transmission of nonautonomous contact guidance information between neighboring cells. Here, we explore these phenomena by quantifying the migratory response of confluent monolayers of epithelial and fibroblast cells to contact guidance cues provided by grooved topography. We show that, in both sparse clusters and confluent sheets, individual cells are contact-guided by grooves and show more coordinated behavior on grooved versus flat substrates. Furthermore, we demonstrate both in vitro and in silico that the guidance signal provided by a groove can propagate between neighboring cells in a confluent monolayer, and that the distance over which signal propagation occurs is not significantly influenced by the strength of cell-cell junctions but is an emergent property, similar to cellular streaming, triggered by mechanical exclusion interactions within the collective system.

Low-bias terahertz amplitude modulator based on split-ring resonators and graphene.

Split-ring resonators represent the ideal route to achieve optical control of the incident light at THz frequencies. These subwavelength metamaterial elements exhibit broad resonances that can be easily tuned lithographically. We have realized a design based on the interplay between the resonances of metallic split rings and the electronic properties of monolayer graphene integrated in a single device. By varying the major carrier concentration of graphene, an active modulation of the optical intensity was achieved in the frequency range between 2.2 and 3.1 THz, achieving a maximum modulation depth of 18%, with a bias as low as 0.5 V.