Measurements of diffusion coefficients in 1-D micro- and nanochannels using shear-driven flows

The present paper describes a method for measuring the molecular diffusion coefficient of fluorescent molecules in microfluidic systems. The proposed static shear-driven flow method allows one to perform diffusion measurements in a fast and accurate manner. The method also allows one to work in very thin (i.e. submicron) channels, hence allowing the investigation of diffusion in highly confined spaces. In the deepest investigated channels, the obtained results were comparable to the existing literature values, but when the channel size dropped below the micrometer range, a significant decrease (more than 30%) in molecular diffusivity was observed. The reduction of the diffusivity was most significant for the largest considered molecules (ssDNA oligomers with a size ranging between 25 to 100 bases), but the decrease was also observed for smaller tracer molecules (FITC). This decrease can be attributed to the interactions of the analyte molecules with the channel walls, which can no longer be neglected when the depth of the channel reaches a critical value. The change in diffusivity seems to become more explicit as the molecular weight of the analytes increases.     

High-transmittance liquid crystal cell fabricated using nanoparticle-doped polyimide

We found that we can increase the transmittance of a liquid crystal (LC) cell by doping the alignment material with nanoparticles. We fabricated an LC cell using indium–tin–oxide glass substrates coated with SiO₂-doped polyimide. We confirmed that the transmittance of LC cells fabricated using SiO₂-doped polyimide was higher than that of LC cells fabricated using pure polyimide. To account for the increase of transmittance, we measured the order parameter of the fabricated LC cells and investigated the surface morphology of the alignment layer using atomic force microscopy.     

Bonding mechanisms of laser‐fabricated titanium/polyimide and titanium coated glass/polyimide microjoints

In this study, two bimaterial joining systems, namely, titanium coated glass/polyimide (TiGPI) and titanium/polyimide (TiPI) are considered. The joints were prepared by employing transmission type laser‐joining procedure. Both the TiGPI and TiPI bimaterial systems were subjected to tensile loading using a microtester, and failure loads per unit bond length were documented. The average failure strengths of the TiPI and TiGPI samples were found to be 5.1 and 7.3 N/mm, respectively. It is thus clear from the failure data that the TiGPI joints are stronger (1.4 times) than the TiPI joints although same chemical bonds between titanium and polyimide (PI) exist for both the systems. It is thus believed that material surface morphology has contributed to such variation in the microjoint strengths. Later, atomic force microscopy (AFM) of titanium surfaces of both titanium coated glass and titanium foil was performed, and was observed that they had root mean squared (RMS) surface roughnesses of 220 and 55 nm, respectively. The surface roughness provides improved surface contact area, number of chemical bonds, and mechanical interlocking that may have resulted in higher bond strength for the TiGPI system. Copyright © 2007 John Wiley & Sons, Ltd.     

Slip flow in graphene nanochannels

We investigate the hydrodynamic boundary condition for simple nanofluidic systems such as argon and methane flowing in graphene nanochannels using equilibrium molecular dynamics simulations (EMD) in conjunction with our recently proposed method [J. S. Hansen, B. D. Todd, and P. J. Daivis, Phys. Rev. E 84, 016313 (2011)]. We first calculate the fluid-graphene interfacial friction coefficient, from which we can predict the slip length and the average velocity of the first fluid layer close to the wall (referred to as the slip velocity). Using direct nonequilibrium molecular dynamics simulations (NEMD) we then calculate the slip length and slip velocity from the streaming velocity profiles in Poiseuille and Couette flows. The slip lengths and slip velocities from the NEMD simulations are found to be in excellent agreement with our EMD predictions. Our EMD method therefore enables one to directly calculate this intrinsic friction coefficient between fluid and solid and the slip length for a given fluid and solid, which is otherwise tedious to calculate using direct NEMD simulations at low pressure gradients or shear rates. The advantages of the EMD method over the NEMD method to calculate the slip lengths/flow rates for nanofluidic systems are discussed, and we finally examine the dynamic behaviour of slip due to an externally applied field and shear rate.     

Diffusioosmotic flows in slit nanochannels

Diffusioosmotic flows of electrolyte solutions in slit nanochannels with homogeneous surface charges induced by electrolyte concentration gradients in the absence of externally applied pressure gradients and potential differences are investigated theoretically. A continuum mathematical model consisting of the strongly coupled Nernst-Planck equations for the ionic species' concentrations, the Poisson equation for the electric potential in the electrolyte solution, and the Navier-Stokes equations for the flow field is numerically solved simultaneously. The induced diffusioosmotic flow through the nanochannel is computed as functions of the externally imposed concentration gradient, the concentration of the electrolyte solution, and the surface charge density along the walls of the nanochannel. With the externally applied electrolyte concentration gradient, a strongly spatially dependent electric field and pressure gradient are induced within the nanochannel that, in turn, generate a spatially dependent diffusioosmotic flow. The diffusioosmotic flow is opposite to the applied concentration gradient for a relatively low bulk electrolyte concentration. However, the electrolyte solution flows from one end of the nanochannel with a higher electrolyte concentration to the other end with a lower electrolyte concentration when the bulk electrolyte concentration is relatively high. There is an optimal concentration gradient under which the flow rate attains the maximum. The induced flow is enhanced with the increase in the fixed surface charge along the wall of the nanochannel for a relatively low bulk electrolyte concentration.     

Electrokinetic transport through nanochannels

This article presents a numerical study of the electrokinetic transport phenomena (electroosmosis and electrophoresis) in a three-dimensional nanochannel with a circular cross-section. Due to the nanometer dimensions, the Boltzmann distribution of the ions is not valid in the nanochannels. Therefore, the conventional theories of electrokinetic flow through the microchannels such as Poisson-Boltzmann equation and Helmholtz-Smoluchowski slip velocity approach are no longer applicable. In the current study, a set of coupled partial differential equations including Poisson-Nernst-Plank equation, Navier-Stokes, and continuity equations is solved to find the electric potential field, ionic concentration field, and the velocity field in the three-dimensional nanochannel. The effects of surface electric charge and the radius of nanochannel on the electric potential, liquid flow, and ionic transport are investigated. Unlike the microchannels, the electric potential field, ionic concentration field, and velocity field are strongly size-dependent in nanochannels. The electric potential gradient along the nanochannel also depends on the surface electric charge of the nanochannel. More counter ions than the coions are transported through the nanochannel. The ionic concentration enrichment at the entrance and the exit of the nanochannel is completely evident from the simulation results. The study also shows that the flow velocity in the nanochannel is higher when the surface electric charge is stronger or the radius of the nanochannel is larger.     

Spontaneous polarization and electro-optic behaviour of a ferroelectric liquid crystal cell fabricated with polyimide Langmuir-Blodgett films

The spontaneous polarization and electro-optic response of ferroelectric liquid crystals (FLCs) were investigated in a cell fabricated with a polyimide alignment layer coated by the Langmuir-Blodgett method. The surface properties of the cured polyimide layers were monitored by contact angle measurement, and by FTIR spectroscopy and AFM for the orientation and surface roughness, respectively. The apparent spontaneous polarization of an FLC determined in a practical sandwich-cell depended on various conditions such as cell thickness, cooling rate from the smectic A to chiral smectic C phase, and deposition pressure. Electro-optic response and decay times of FLCs were also measured. Furthermore, the ions in the FLC mixture reduced the magnitude of the effective electric field, but had no effect at high frequency.     

Hairpin polymer unfolding in square nanochannels

The unfolding dynamics of a flexible hairpin polymer inserted in a square nanochannel is studied using Brownian dynamics simulations of the bead‐spring model. Because the hairpin polymer is not an equilibrium configuration, the molecule starts unfolding until it reaches a stretched configuration inside the tube. We study the effect of varying the channel height and width D, and the number of monomers N in the folded arm on the unfolding times. We show that for square nanochannels, the unfolding time scales as DN2, for small values of D. The unfolding relaxation dynamics obeys similar mechanisms described in the escaping dynamics of partially inserted polymers in cylindrical nanotubes. We also show that the velocity of the polymer center of mass scales as D^?1, in agreement with DNA unfolding experiments in solid‐state nanochannels and recent computational simulations. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1411–1418     

Pretilt angle of liquid crystals and liquid-crystal alignment on microgrooved polyimide surfaces fabricated by soft embossing method

In this study, the soft embossing method is proposed to fabricate periodical microgrooved structure on polyimide surfaces. These microgrooved polyimide surfaces are assembled to form liquid-crystal cells. It is found that the director of liquid crystals uniformly aligns along the groove direction even when the groove width is as high as 3 microm. The anchoring energy of these microgrooved polyimide surfaces is higher than that of the typical rubbed surfaces. The pretilt angle of liquid crystals is adjusted by tuning the surface polarity of the polyimide alignment layer, which is identified by the advancing contact angle of water. The surface polarity of polyimide alignment layers is manipulated by simply mixing two kinds of polyimide: a more hydrophilic one and a more hydrophobic one. It is found that the pretilt angle of liquid crystals increases along with the advancing contact angle of water on the alignment layer under the condition of a fixed surface topography.     

Enantioselective recognition in biomimetic single artificial nanochannels

Efficient enantiomer discrimination with a convenient system remains a challenge in the fields of biochemistry, medical science, and pharmaceutics. Here we report a simple enantioselective sensing device based on a single artificial β-cyclodextrin-modified nanochannel system. This nanodevice shows highly selective recognition of histidine enantiomers through monitoring of ionic current signatures.     

Electrokinetic transport and separations in fluidic nanochannels

This article presents a summary of theory, experimental studies, and results for the electrokinetic transport in small fluidic nanochannels. The main focus is on the effect of the electric double layer on the EOF, electric current, and electrophoresis of charged analytes. The double layer thickness can be of the same order as the width of the nanochannels, which has an impact on the transport by shaping the fluid velocity profile, local distributions of the electrolytes, and charged analytes. Our theoretical consideration is limited to continuum analysis where the equations of classical hydrodynamics and electrodynamics still apply. We show that small channels may lead to qualitatively new effects like selective ionic transport based on charge number as well as different modes for molecular separation. These new possibilities together with the rapid development of nanofabrication capabilities lead to an extensive experimental effort to utilize nanochannels for a variety of applications, which are also discussed and analyzed in this review.     

Biomimetic smart nanopores and nanochannels

Nature provides a huge range of biological materials, just as ion channels, with various smart functions over millions of years of evolution, and which serve as a big source of bio-inspiration for biomimetic materials. In this critical review, a strategy for the design and synthesis of biomimetic smart nanopores and nanochannels is presented and put into context with recent progress in this rapidly growing field from biological, inorganic, organic to composite nanopore and nanochannel materials, which can respond to single/multiple external stimuli, e.g., pH, temperature, light, and so on. This review is intended to utilize a specific responsive behavior for regulating ionic transport properties inside the single nanopore or nanochannel as an example to demonstrate the feasibility of the design strategy, and provide an overview of this fascinating research field (109 references).     

Formation of liquid menisci in flexible nanochannels

In the present paper a novel mechanochemical process for the elimination of organic pollutants dissolved in water is proposed. In this regard, phenol aqueous solutions (100 mg L⁻¹) were ball-milled for 0, 12, 18, 24, 36, 48, and 72 h with and without a well-characterized (XRD, SEM, and N₂ Adsorption), rutile powder catalyst and the reaction products analyzed with UV and GC/MS. It was found that when the catalyst was not included in the process, phenol was not affected, but when it was included, phenol was decomposed. The catalyst itself did not change and the reaction follows a pseudo-first-order kinetics. Besides, intermediates which are characteristic of the OH radical mechanism were found in the reaction products. Then, a mechanism similar to those accepted for other advanced oxidation processes was proposed. The value measured for the pseudo-first-order reaction constant was very low, indicating that the reported process is inefficient. Nevertheless, this problem could be solved by applying catalysts consisting of particles with smaller diameters.     

Micro-imaging of transient guest profiles in nanochannels

Zeolites of type ferrierite are exploited as a host system for monitoring the evolution of guest concentration (methanol) in nanoporous host materials upon adsorption. Additional transport resistances at the crystal surface have been removed so that uptake is exclusively controlled by the diffusion resistance of the pore space. Since the crystal shape deviates from a simple parallelepiped, the primary imaging data do not immediately reflect true local concentrations. A simple algorithm is developed which overcomes this complication. The determined transient concentration profiles ideally comply with the requirements for the application of the Boltzmann-Matano integration method for determining diffusivities. The resulting diffusivities (along the direction of the "10-ring channels") are found to exceed those along the 8-ring channels by three orders of magnitude.     

Formation of nanostructured polymer filaments in nanochannels

We describe the use of hard etching methods to create nanodimensional channels and their use as templates for the formation of polymer filament arrays with precise dimensional and orientational control in a single integrated step. The procedure is general as illustrated by the radical, coordination, and photochemical polymerizations that were performed in these nanochannels. The nanochannel templates (20 nm high, 20-200 nm wide, and 100 mum long) were fabricated by the combined use of electron-beam lithography and a sacrificial metal line etching technique. Radical polymerization of acrylates, metal-catalyzed polymerization of norbornene, and photochemical polymerization of 1,4-diiodothiophene were carried out in these nanochannels. The polymers grown follow the dimensions and orientation of the channels, and the polymer filaments can be released without breaking. The approach opens up the possibility of just-in-place manufacturing and processing of patterns and devices from nanostructured polymers using well-established polymer chemistry.     

Transformation of 1-D Chiral-chained Titanium Phosphate to 2-D Layer Structure Through a 1-D Zigzag Chain

The transformation of titanium phosphate from 1-D chiral- chain(JTP-A) to 2-D layer( TP-J1 ) has been carefully investigated. Through a hydrolysis-condensation self-assembly pathway, the crystals of TP-J1 can be obtained from the JTP-A phase under hydrothermal conditions. An intermediate material with zigzag chain during the transformation was observed by XRD characterization. A hypothesis of the transformation mechanism is also described in this article. It is noteworthy that ethylenediamine plays an important role in the transformation.     

ESR study of molecular orientation and dynamics of TEMPO derivatives in CLPOT 1D nanochannels

The molecular orientations and dynamics of 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl (TEMPO) radical derivatives with large substituent groups at the 4‐position (4‐X‐TEMPO) in the organic one‐dimensional nanochannels within the nanosized molecular template 2,4,6‐tris(4‐chlorophenoxy)‐1,3,5‐triazine (CLPOT) were examined using ESR. The concentrations of guest radicals, including 4‐methoxy‐TEMPO (MeO‐TEMPO) or 4‐oxo‐TEMPO (TEMPONE), in the CLPOT nanochannels in each inclusion compound (IC) were reduced by co‐including 4‐substituted‐2,2,6,6‐tetramethylpiperidine (4‐R‐TEMP) compounds at a ratio of 1 : 30–1 : 600. At higher temperatures, the guest radicals in each IC underwent anisotropic rotational diffusion in the CLPOT nanochannels. The rotational diffusion activation energy, E_a, associated with MeO‐TEMPO or TEMPONE in the CLPOT nanochannels (6–7 kJ mol^?1), was independent of the size and type of substituent group and was similar to the E_a values obtained for TEMPO and 4‐ hydroxy‐TEMPO (TEMPOL) in our previous study. However, in the case in which TEMP was used as a guest compound for dilution (spacer), the tilt of the rotational axis to the principal axis system of the g ‐tensor, and the rotational diffusion correlation time, τ_R, of each guest radical in the CLPOT nanochannels were different from the case with other 4‐R‐TEMP. These results indicate the possibility of controlling molecular orientation and dynamics of guest radicals in CLPOT ICs through the appropriate choice of spacer. Copyright © 2016 John Wiley & Sons, Ltd.     

Fluid transport in nanochannels induced by temperature gradients

We investigate the mechanisms of fluid transport driven by temperature gradients in nanochannels through molecular dynamics simulations. It is found that the fluid-wall interaction is critical in determining the flow direction. In channels of very low surface energy, where the fluid-wall binding energy ε(fw) is small, the fluid moves from high to low temperature and the flow is induced by a potential ratchet near the wall. In high surface energy channels, however, the fluid is pumped from low to high temperature and the pressure drop caused by the temperature gradient is the major driving force. In addition, as the fluid-wall interaction is strengthened, the flow flux assumes a maximum, where ε(fw) is close to the lower temperature T(L) of the channel and ε(fw)/kT(L) ≈ 1 is roughly satisfied.