Saif A. Khan

Transport and reaction in microscale segmented gas–liquid flow

We use micro particle image velocimetry (microPIV) and fluorescence microscopy techniques to characterize microscale segmented gas-liquid flow at low superficial velocities relevant for chemical reactions with residence times of up to several minutes. Different gas-liquid microfluidic channel networks of rectangular cross section are fabricated in poly(dimethylsiloxane) (PDMS) using soft lithography techniques. The recirculation motion in the liquid segments associated with gas-liquid flows as well as the symmetry characteristics of the recirculations are quantified for straight and meandering channel networks. Even minor surface roughness effects and the compressibility of the gas phase induce loss of symmetry and enhance mixing across the centerline in straight channels. Mixing is further accelerated in meandering channels by the periodic switching of recirculation patterns across the channel center. We demonstrate a new, piezoelectrically activated flow injection technique for determining residence time distributions (RTDs) of fluid elements in multiphase microfluidic systems. The results confirm a narrowed liquid phase RTD in segmented flows in comparison to their single-phase counterparts. The enhanced mixing and narrow RTD characteristics of segmented gas-liquid flows are applied to liquid mixing and in sol-gel synthesis of colloidal nanoparticles.

Droplet-Based Microfluidic Synthesis of Anisotropic Metal Nanocrystals

A droplet-based microfluidic method for the preparation of anisotropic gold nanocrystal dispersions is presented. Gold nanoparticle seeds and growth reagents are dispensed into monodisperse picoliter droplets within a microchannel. Confinement within small droplets prevents contact between the growing nanocrystals and the microchannel walls. The critical factors in translating macroscale flask-based methods to a flow-based microfluidic method are highlighted and approaches are demonstrated to flexibly fine tune nanoparticle shapes into three broad classes: spheres/spheroids, rods, and extended sharp-edged structures, thus varying the optical resonances in the visible-near-infrared (NIR) spectral range.

Monodisperse polymeric ionic liquid microgel beads with multiple chemically switchable functionalities.

We present simple, inexpensive microfluidics-based fabrication of highly monodisperse poly(ionic liquid) microgel beads with a multitude of functionalities that can be chemically switched in facile fashion by anion exchange and further enhanced by molecular inclusion. Specifically, we show how the exquisite control over bead size and shape enables extremely precise, quantitative measurements of anion- and solvent-induced volume transitions in these materials, a crucial feature driving several important applications. Next, by exchanging diverse anions into the synthesized microgel beads, we demonstrate stimuli responsiveness and a multitude of novel functionalities including redox response, controlled release of chemical payloads, magnetization, toxic metal removal from water, and robust, reversible pH sensing. These chemically switchable stimulus-responsive beads are envisioned to open up a vast array of potential applications in portable and preparative chemical analysis, separations and spatially addressed sensing.

Controlling bubbles using bubbles—microfluidic synthesis of ultra-small gold nanocrystals with gas-evolving reducing agents

Microfluidic wet-chemical synthesis of nanoparticles is a growing area of research in chemical microfluidics, enabling the development of continuous manufacturing processes that overcome the drawbacks of conventional batch-based synthesis methods. The synthesis of ultra-small (<5 nm) metallic nanocrystals is an interesting area with many applications in diverse fields, but is typically very challenging to accomplish in a microfluidics-based system due to the use of a strong gas-evolving reducing agent, aqueous sodium borohydride (NaBH(4)), which causes uncontrolled out-gassing and bubble formation, flow disruption and ultimately reactor failure. Here we present a simple method, rooted in the concepts of multiphase mass transfer that completely overcomes this challenge-we simply inject a stream of inert gas bubbles into our channels that essentially capture the evolving gas from the reactive aqueous solution, thereby preventing aqueous dissolved gas concentration from reaching the solubility threshold for bubble nucleation. We present a simple model for coupled mass transfer and chemical reaction that adequately captures device behaviour. We demonstrate the applicability of our method by synthesizing ultra-small gold nanocrystals (<5 nm); the quality of nanocrystals thus synthesized is further demonstrated by their use in an off-chip synthesis of high-quality gold nanorods. This is a general approach that can be extended to a variety of metallic nanomaterials.

Inkjet printing and release of monodisperse liquid crystal droplets from solid surfaces.

Recently, liquid crystal (LC) droplets in aqueous solutions have become a new platform for chemical and biological sensing applications. In this work, we present a two-step method to generate monodisperse LC droplets in aqueous solutions for sensing applications. In the first step, we exploit inkjet printing to dispense uniform LC droplets on a solid surface. Uniform LC droplets, ranging from 35 to 136 μm in diameter, can be prepared by printing multiple times on the same spot. In the second step, we flush the LC droplets with a stream of aqueous solution in an open rectangular channel. Factors that determine the polydispersity of the LC droplets include flow rates and surface wettability. Under appropriate experimental conditions (i.e., when the surface is glass and the flow rate is sufficiently high), the LC droplets can be lifted off completely and carried away by the solution, forming free LC droplets (15-62 μm in diameter). These free LC droplets can respond to a chemical reaction and change their optical textures uniformly.

Modulation of surface wettability of superhydrophobic substrates using Si nanowire arrays and capillary-force-induced nanocohesion

We describe a new scalable method to fabricate large-area hybrid superhydrophobic surfaces with selective adhesion properties on silicon (Si) nanowire array substrates by exploiting liquid-medium-dependent capillary-force-induced nanocohesion. Gold (Au) nanoparticles were deposited on Si by glancing angle deposition followed by metal-assisted chemical etching of Si to form Si nanowire arrays. The surfaces were dried in either deionized (DI) water, 2-propanol or methanol to vary the capillary forces exerted on the Si nanowires during the drying process in order to tune the extent of clustering of nanowires and hence the adhesion properties of the resulting superhydrophobic surfaces. Here, we exploit the combined effects of surface tension and Youngs contact angle to modulate the degree of clustering of the Si nanowires during capillary-force-induced nanocohesion. These surfaces were chemically modified and rendered hydrophobic by fluorosilane deposition. Drying in DI water resulted in small clusters of nanowires which produce a low-hysteresis superhydrophobic surface that mimics a lotus leaf. Drying in methanol resulted in large nanowire clusters that lead to a high-hysteresis superhydrophobic surface. Further, we demonstrate the ability to fabricate both small and large nanowire clusters by controlling the drying of the nanowire arrays in order to selectively define and modulate adhesion of water on the same superhydrophobic substrate. The simplicity of our process to tune surface wettability on single substrates paves the way for future applications in lab-on-chip devices and platforms for chemical and biological analyses.

UV-Defined Flat PDMS Stamps Suitable for Microcontact Printing

We report a simple method of creating well-defined micropatterns on the surface of a flat PDMS stamp, making it suitable for microcontact printing of proteins. This method only requires a UV lamp (254 nm) and a TEM grid (as a photomask) to modify the surface of PDMS for creating desired micropatterns. By using the UV-modified stamp, a printed protein micropattern that resembles the original TEM grid can be obtained. Surprisingly, unlike the oxygen-plasma-treated PDMS, the UV-modified flat stamp is also long-lasting (>1 week). The method reported herein is very economical for microcontact printing applications because expensive silicon masters and microstructured PDMS are no longer required.

Radiation stability of graphene under extreme conditions

In this letter, we report radiation stability of graphene under extreme condition of high energy density generated by 150 MeV Au ion irradiation. The experiment reveals that graphene is radiation resistant for irradiation at 1014 ions/cm2 of 150 MeV Au ions. It is significant to note that annealing effects are observed at lower fluences whereas defect production occurs at higher fluences but significant crystallinity is retained. Our results demonstrate applicability of graphene based devices in radiation environment and space applications.

Swift heavy ion irradiation of ZnO nanoparticles embedded in silica: Radiation-induced deoxidation and shape elongation

ZnO nanoparticles (NPs) embedded in amorphous SiO2 were irradiated with 200 MeV Xe14+ swift heavy ions (SHIs) to a fluence of 5.0 × 1013 ions/cm2. Optical linear dichroism was induced in the samples by the irradiation, indicating shape transformation of the NPs from spheres to anisotropic ones. Transmission electron microscopy observations revealed that some NPs were elongated to prolate shapes; the elongated NPs consisted not of ZnO but of Zn metal. The SHI irradiation induced deoxidation of small ZnO NPs and successive shape elongation of the deoxidized metal NPs.

Co-Micellization Behavior in Poloxamers: Dissipative Particle Dynamics Study

Dissipative particle dynamics simulations are applied to investigate co-micellization behavior for binary mixtures of Poloxamers in dilute aqueous solution. In view of block length similarity/dissimilarity, four representative mixture cases are considered: F127/P123, F127/P105, P123/P84, and F127/L64. With appropriate interaction parameters, the simulations enable us to examine the formation of micelles, their types, size, shape, and composition. In the investigated concentration range, we find that pure and mixed micelles, both ellipsoidal, always coexist for all cases. At similar concentrations, both species form pure micelles of their own together with mixed micelles. In the case of F127/L64, it is found that the L64 chains are involved in the mixed micelles, even when the L64 concentration is below its CMC. The fraction of L64 involved in the mixed micelles is lower as compared to the other systems studied. For all cases, the proportion of mixed micelles can be increased when the two polymer species have similar concentrations. Moreover, shorter chains may prefer to straddle the core and corona in the region of ellipsoidal interface that is closer to the center of mixed micelle.