Phase Diagram Characterization Using Magnetic Beads as Liquid Carriers

Magnetic beads with ~1.9 &#181;m average diameter were used to transport microliter volumes of liquids between contiguous liquid segments with a tube for ...

University of Cincinnati

The development of novel photonic devices which incorporate biological materials is strongly tied to the development of thin film forming processes. Solution-based ("wet") processes when used with biomaterials in device fabrication suffer from dissolution of underlying layers, incompatibility with clean environment, inconsistent film properties, etc. We have investigated ultra-high-vacuum molecular beam deposition of surfactant-modified deoxyribonucleic acid (DNA). We have obtained effective deposition rates of approximately 0.1-1 A/s, enabling reproducible and controllable deposition of nanometer-scale films.

Molecular beam deposition of DNA nanometer films.

Bright blue-light emission at 410 nm is observed from Mg(2+)-doped GaN nanoparticles prepared by the nitridation of Ga(2)MgO(4) nanoparticles at 950 degrees C. The sintering of these nanoparticles during high-temperature nitridation was prevented by mixing the Ga(2)MgO(4) precursor nanoparticles with La(2)O(3) as an inert matrix before the nitridation process. The Mg(2+)-doped GaN nanoparticles were isolated from the matrix by etching with 10 % nitric acid. The Mg(2+)-doped GaN nanoparticles were characterized by photoluminescence, atomic force microscopy, X-ray diffraction, and IR analyses.

Mg 2+-doped GaN nanoparticles as blue-light emitters: a method to avoid sintering at high temperatures.

Control of surface wetting properties to produce strongly hydrophobic or hydrophilic effects is at the heart of many macro- and microfluidic applications. In this work, we have investigated coaxial electrospinning to produce core-sheath-structured nano/microfibers that combine different properties from individual core and sheath materials. Teflon AF is an amorphous fluoropolymer that is widely utilized as a hydrophobic material. Hydrophobic fluoropolymers are normally not electrospinnable because their low dielectric constant prevents sufficient charging for a solution to be electrospun. The first Teflon electrospun fibers are reported using coaxial electrospinning with Teflon AF sheath and poly(epsilon-caprolactone) (PCL) core materials. Using these core/sheath fibers, superhydrophobic and oleophobic membranes have been successfully produced. These coaxial fibers also preserve the core material properties as demonstrated with mechanical tensile tests. The fact that a normally nonelectrospinnable material such as Teflon AF has been successfully electrospun when combined with an electrospinnable core material indicates the potential of coaxial electrospinning to provide a new degree of freedom in terms of material combinations for many applications.

Superhydrophobic and oleophobic fibers by coaxial electrospinning.

Highly efficient preconcentration is a crucial prerequisite to the identification of important protein biomarkers with extremely low abundance in target biofluids. In this work, poly(dimethylsiloxane) microchips integrated with 10 nm polycarbonate nanopore membranes were utilized as high-speed protein accumulators. Double-sided injection control of electrokinetic fluid flow in the sample channel resulted in highly localized protein accumulation at a very sharp point in the channel cross point. This greatly enhanced the ability to detect very low levels of initial protein concentration. Fluorescein labeled human serum albumin solutions of 30 and 300 pM accumulated to 3 and 30 microM in only 100 s. Initial solutions as low as 0.3 and 3 pM could be concentrated within 200 s to 0.3 and 3 microM, respectively. This demonstrates a approximately 10(5)-10(6) accumulation factor, and an accumulation rate as high as 5000/sec, yielding a >10x improvement over most results reported to date.

High speed nanofluidic protein accumulator.

For the purpose of immunoassay, electrospun membranes can be thought as the threadlike self-assembling of nano/microbeads. Nonwoven membranes of electrospun poly(epsilon-caprolactone) (PCL) fibers display excellent tenacity, flexibility and suitable surface energy. These PCL membranes exhibit easy handling in air, fast spreading, and wetting in aqueous solution, and rapid adsorption of protein molecules by hydrophobic interaction. After a fold-and-press process, the membrane porosity was reduced from approximately 75% to less than 10%, whereas the thickness increased from 5.3 to 280 microm. The resulting fluorescence signal from adsorbed protein increased>120x. With anti-HSA and HSA-FITC as an immunoassay model, a linear detection range from 500 ng/mL down to 1 ng/mL is obtained, with a detection of limit (LOD) of approximately 0.08 ng/mL. By comparison, conventional nitrocellulose and a 24.3 microm PCL fiber electrospun membrane displayed a much higher LOD of approximately 100 ng/mL. Immunoassay on free-standing electrospun membrane successfully combines the low-cost and simplicity of conventional membrane immunoassay, with the fast reaction speed and high sensitivity characteristic of magnetic nano/microbeads bioassays.

Immunoassay on free-standing electrospun membranes.

The use of paper as a material for various device applications (such as microfluidics and energy storage) is very attractive given its flexibility, versatility, and low cost. Here we demonstrate that electrowetting (EW) devices can be readily fabricated on paper substrates. Several categories of paper have been investigated for this purpose, with the surface coating, roughness, thickness, and water uptake, among the most important properties. The critical parameter for EW devices is the water contact angle (CA) change with applied voltage. EW devices on paper exhibit characteristics very close to those of conventional EW devices on glass substrates. This includes a large CA change in oil ambient (90-95°), negligible hysteresis (∼2°), and fast switching times of ∼20 ms. These results indicate the promise of low-cost paper-based EW devices for video rate flexible e-paper on paper.

Electrowetting on paper for electronic paper display.

A novel approach to control the area of anchor-free droplet interface bilayer (DIB) lipid membranes is presented. Unsupported DIB lipid membranes are formed at the interface of phospholipid-coated aqueous droplets dispensed in dodecane oil. Using electrodes inserted into the droplets, an external voltage is applied which modulates the effective DIB area. Electrical (capacitance or current) and optical (imaging of DIB lateral length) recordings were simultaneously performed. Alpha-hemolysin (αHL) single channel insertions into the DIB were recorded. Currents across the DIB were measured as a function of voltage and αHL concentration in the droplets. Nonlinear response is observed for current, DIB lateral length and area, and capacitance with respect to voltage. Voltage induced changes in interfacial tension modulated the DIB-oil contact angle and the membrane contact length, which provided control of membrane dimensions. Comparison of these results is made to the electrowetting effect, which is also governed by effect of voltage on the interfacial tension. This approach provides active control of the number of ion channels inserted into the DIB.

Voltage control of droplet interface bilayer lipid membrane dimensions.

Electrospun fibers consisting of poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT/PSS) and poly(ethylene oxide) (PEO) have been used to successfully encapsulate and stabilize thylakoid membrane vesicles isolated from spinach. Light-driven electronic properties were measured. Fibers with immobilized thylakoids show higher electrical conductivity compared with fibers without thylakoids under white light conditions. This is attributed to the electron-generating photosynthetic reactions from the thylakoids. Electron and optical microscopy show the presence of thylakoid vesicles within the fibers using lipid-specific stains. After electrospinning into fibers, the thylakoid vesicles still exhibit an ability to produce a light-driven electron gradient, indicating that activity is preserved during the electrospinning process. These electrospun fibers provide an excellent example of incorporating photosynthetic function into an artificial system.

Immobilization of stable thylakoid vesicles in conductive nanofibers by electrospinning.

A novel dual drug delivery system is presented using triaxial structured nanofibers, which provides different release profiles for model drugs separately loaded in either the sheath or the core of the fiber. Homogenous, coaxial and triaxial fibers containing a combination of materials (PCL, polycaprolactone; PVP, polyvinylpyrrolidone) were fabricated. The drug release profiles were simulated using two color dyes (KAB, keyacid blue; KAU, keyacid uranine), whose release in physiological solution was measured using optical absorption as a function of time. To reach the level of 80% release of encapsulated dye from core, triaxial fibers with a PCL intermediate layer exhibited a ~24× slower release than that from coaxial fibers. At the same time, the hygroscopic sheath layer of the triaxial fibers provided an initial burst release (~ 80% within an hour) of a second dye as high as that from conventional single and coaxial fibers. The triaxial fiber membrane provides both a quick release from the outer sheath layer for short-term treatment and a sustained release from the fiber core for long-term treatment. The intermediate layer between inner core and outer sheath acts as a barrier to prevent leaching from the core, which can be especially important when the membranes are used in wet application. The formation of tri/multiaxially electrospun nanofibrous membranes will be greatly beneficial for biomedical applications by enabling different release profiles of two different drugs from a membrane.

Triaxial electrospun nanofiber membranes for controlled dual release of functional molecules.

Pentacene-based organic thin-film transistors (OTFTs) were fabricated on several types of flexible substrate: commercial photo paper, ultra-smooth specialty paper and ultra-thin (100 μM) flexible glass. The transistors were fabricated entirely through dry-step processing. The transconductance and field-effect mobility of OTFTs on photo paper reached values of ∼0.52 mS m(-1) and ∼ 0.1 cm(2) V (-1) s(-1), respectively. Preliminary results on the lifetime of OTFTs on photo paper yielded stable transconductance and mobility values over a period of more than 250 h. The comparable characteristics of OTFTs fabricated on widely available, low cost paper and high quality expensive liquid crystal display glass indicate the potential importance of cellulose-based electronic devices.

Pentacene organic thin-film transistors on flexible paper and glass substrates.

Organic light-emitting diodes (OLED) were fabricated on flexible and transparent reconstituted cellulose obtained from wood pulp. Cellulose is naturally available, abundant, and biodegradable and offers a unique substrate alternative for the fabrication of flexible OLEDs. Transparent cellulose material was formed by dissolution of cellulose in an organic solvent (dimethyl acetamide) at elevated temperature (165 °C) in the presence of a salt (LiCl). The optical transmission of 40-μm thick transparent cellulose sheet averaged 85% over the visible spectrum. High brightness and high efficiency thin film OLEDs were fabricated on transparent cellulose films using phosphorescent Ir(ppy)3 as the emitter material. The OLEDs achieved current and luminous emission efficiencies as high as 47 cd A(-1) and 20 lm W(-1), respectively, and a maximum brightness of 10,000 cd m(-2).

High brightness phosphorescent organic light emitting diodes on transparent and flexible cellulose films.

Magnetic beads (MBs) with ∼1.9 μm average diameter were used to transport specific microliter-scale volumes of liquids between adjacent reservoirs within a closed tube under the influence of a magnetic field. The tube's inner surface is coated with a hydrophobic layer, enabling the formation of a surface tension valve by inserting an air gap between reservoirs. This transfer process was implemented by keeping the MBs stationary with a fixed external magnet while the liquid reservoirs were translated by a computer-controlled syringe pump system. The magnet induces the aggregation of MBs in a loosely packed cluster (void volume ∼90-95%) against the tube's inner wall. The liquid trapped in the MB cluster is transported across the air gap between reservoirs. Fluorescence intensity from a dye placed in one reservoir is used to measure the volume of liquid transferred between reservoirs. The carry-over liquid volume is controlled by the mass of the MBs within the device. The typical volume of liquid carried by the MB cluster is ∼2 to 3 μL/mg of beads, allowing the use of small samples. This technique can be used to study the effect of small compositional variation on the properties of fluid mixtures. The feasibility of this "lab-in-tube" approach for binary phase diagram determination in a water-surfactant (C12E5) system was demonstrated.

Magnetic particles as liquid carriers in the microfluidic lab-in-tube approach to detect phase change.

We report on the use of nucleic acid bases (NBs) in organic light emitting diodes (OLEDs). NBs are small molecules that are the basic building blocks of the larger DNA polymer. NBs readily thermally evaporate and integrate well into the vacuum deposited OLED fabrication. Adenine (A) and thymine (T) were deposited as electron-blocking/hole-transport layers (EBL/HTL) that resulted in increases in performance over the reference OLED containing the standard EBL material NPB. A-based OLEDs reached a peak current efficiency and luminance performance of 48 cd/A and 93,000 cd/m(2), respectively, while T-based OLEDs had a maximum of 76 cd/A and 132,000 cd/m(2). By comparison, the reference OLED yielded 37 cd/A and 113,000 cd/m(2). The enhanced performance of T-based devices is attributed to a combination of energy levels and structured surface morphology that causes more efficient and controlled hole current transport to the emitting layer.

DNA bases thymine and adenine in bio-organic light emitting diodes.

Naturally occurring biomolecules have increasingly found applications in organic electronics as a low cost, performance-enhancing, environmentally safe alternative. Previous devices, which incorporated DNA in organic light emitting diodes (OLEDs), resulted in significant improvements in performance. In this work, nucleobases (NBs), constituents of DNA and RNA polymers, are investigated for integration into OLEDs. NB small molecules form excellent thin films by low-temperature evaporation, enabling seamless integration into vacuum deposited OLED fabrication. Thin film properties of adenine (A), guanine (G), cytosine (C), thymine (T), and uracil (U) are investigated. Next, their incorporation as electron-blocking (EBL) and hole-blocking layers (HBL) in phosphorescent OLEDs is explored. NBs affect OLED performance through charge transport control, following their electron affinity trend: G < A < C < T < U. G and A have lower electron affinity (1.8-2.2 eV), blocking electrons but allowing hole transport. C, T, and U have higher electron affinities (2.6-3.0 eV), transporting electrons and blocking hole transport. A-EBL-based OLEDs achieve current and external quantum efficiencies of 52 cd A(-1) and 14.3%, a ca. 50% performance increase over the baseline device with conventional EBL. The combination of enhanced performance, wide diversity of material properties, simplicity of use, and reduced cost indicate the promise of nucleobases for future OLED development.

Exploring the Potential of Nucleic Acid Bases in Organic Light Emitting Diodes.

The integration of organic light emitting diodes (OLEDs) as excitation light sources for quantum dot-based fluorescent lateral flow immunoassay systems (LFIA) was investigated. This approach has the potential to deliver a sensitive visible detection scheme for low-cost, disposable lab-on-chip point-of-care (POC) diagnosis system. Thin film phosphorescent green OLEDs fabricated on plastic substrates were integrated on-chip to excite the test line of a quantum dot-based LFIA (QD-LFIA). OLEDs were fabricated by sequential deposition of organic thin films (total of ~100nm) onto ITO-coated PET substrates. CdSe/ZnS QDs emitting at 655nm and Au nanoparticles (NP - 10nm size) conjugated antibodies were used for the fluorescence QD-LFIA and conventional reflection-mode Au NP-LFIA, respectively. Thin plastic color light filters were integrated for filtering the excitation light source and, thereby, increasing the contrast of the emitted light for optimized visual detection. Integration of the OLED and color filters with the analytical membrane was achieved using adhesive techniques facilitated by the planar nature of the layers, which suggests possible large scale manufacturing using roll-to-roll processing. Gray scale analysis from digital images captured with a digital camera was used to quantify the visual sensitivity. The signal intensity, signal-to-noise ratio (SNR) and the limit of detection (LOD) of OLED integrated QD-LFIAs were compared to Au NP LFIAs. OLED QD-LFIA exhibited superior performance in all signal aspects: 7-8× higher signal intensity and SNR, and a 7× lower LOD of 3nM (measured at S/N=3). These results demonstrate the potential of OLED-integrated in LFIA devices for obtaining sensitive, fast and low-cost POC diagnostics.

Integrated OLED as excitation light source in fluorescent lateral flow immunoassays.

Electrospun polyacrylonitrile (PAN) based carbon nanofibers (CNFs) have attracted intense attention due to their easy processing, high carbon yield, and robust mechanical properties. In this work, a CNF modified glassy carbon (GC) electrode that was coated with Nafion polymer was evaluated as a new electrode material for the simultaneous determination of trace levels of heavy metal ions by anodic stripping voltammetry (ASV). Pb(2+) and Cd(2+) were used as a representative system for this initial study. Well-defined stripping voltammograms were obtained when Pb(2+) and Cd(2+) were determined individually and then simultaneously in a mixture. Compared to a bare GC electrode, the CNF/Nafion modified GC (CNF/Nafion/GC) electrode improved the sensitivity for lead detection by 8-fold. The interface properties of the CNF/Nafion/GC were characterized by electrochemical impedance spectroscopy (EIS), which showed the importance of the ratio of CNF/Nafion on electrode performance. Under optimized conditions, the detection limits are 0.9 and 1.5 nM for Pb(2+) and Cd(2+), respectively.

Andrew J. Steckl

Department of Electrical Engineering and Computing Systems

University of Cincinnati

Phase Diagram Characterization Using Magnetic Beads as Liquid Carriers

Andrew J. Steckl

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Electrical Engineering and Computing Systems

University of Cincinnati

Phase Diagram Characterization Using Magnetic Beads as Liquid Carriers

Department of Electrical Engineering and Computing Systems