Person: Glavan, Ana
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Glavan
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Ana
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Glavan, Ana
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Publication Rapid fabrication of pressure-driven open-channel microfluidic devices in omniphobic RF paper(Royal Society of Chemistry (RSC), 2013) Glavan, Ana; Martinez, Ramses V.; Maxwell, E. Jane; Subramaniam, Anand; Nunes, Rui M. D.; Soh, Siowling; Whitesides, GeorgeThis paper describes the fabrication of pressure-driven, open-channel microfluidic systems with lateral dimensions of 45-300 microns carved in omniphobic paper using a craft-cutting tool. Vapor phase silanization with a fluorinated alkyltrichlorosilane renders paper omniphobic, but preserves its high gas permeability and mechanical properties. When sealed with tape, the carved channels form conduits capable of guiding liquid transport in the low-Reynolds number regime (i.e. laminar flow). These devices are compatible with complex fluids such as droplets of water in oil. The combination of omniphobic paper and a craft cutter enables the development of new types of valves and switches, such as “fold” valves and “porous switches,” which provide new methods to control fluid flow.Publication Electroanalytical devices with pins and thread(Royal Society of Chemistry (RSC), 2016) Glavan, Ana; Ainla, Alar; Hamedi, Mahiar Max; Fernández-Abedul, M. Teresa; Whitesides, GeorgeThis work describes the adaptive use of conventional stainless steel pins—used in unmodified form or coated with carbon paste—as working, counter, and quasi-reference electrodes in electrochemical devices fabricated using cotton thread or embossed omniphobic RF paper to contain the electrolyte and sample. For some applications, these pin electrodes may be easier to modify and use than printed electrodes, and their position and orientation can be changed as needed. Electroanalytical devices capable of multiplex analysis (thread-based arrays or 96-well plates) were easily fabricated using pins as electrodes in either thread or omniphobic RF paper.Publication Analytical Devices Based on Direct Synthesis of DNA on Paper(American Chemical Society (ACS), 2016) Glavan, Ana; Niu, Jia; Chen, Zhen; Güder, Firat; Cheng, Chao-Min; Liu, David; Whitesides, GeorgeThis paper addresses a growing need in clinical diagnostics for parallel, multiplex analysis of biomarkers from small biological samples. It describes a new procedure for assembling microarrays of ssDNA and proteins on paper. This method starts with the synthesis of DNA oligonucleotides covalently linked to paper, and proceeds to generate DNA arrays capable of simultaneously capturing DNA, DNA-conjugated protein antigens, and DNA-conjugated antibodies. The synthesis of ssDNA oligonucleotides on paper is convenient and effective, with32% of the oligonucleotides cleaved and eluted from the paper substrate being full-length by HPLC for a 32-mer. These ssDNA arrays can be used to detect fluorophore-linked DNA oligonucleotides in solution, and as the basis for DNA-directed assembly of microarrays of DNA-conjugated capture antibodies on paper, detect protein antigens by sandwich ELISAs. Paper-anchored ssDNA arrays with different sequences can be used to assemble paper-based devices capable of detecting DNA and antibodies in the same device, and enable simple microfluidic paper-based devices.Publication Chemical Approaches to the Surface Engineering of Paper and Cellulose-Based Materials for Microfluidics, Electronics and Low-Cost Diagnostics(2016-01-27) Glavan, Ana; Whitesides, George; Aizenberg, Joanna; Cohen, AdamPaper (and other cellulose-based materials such as cotton thread and fabrics) are underexploited as materials for the construction of “high-tech” and “lab-on-a-chip” devices. One major drawback of paper is its tendency to absorb water from the environment and, with wetting, to change its mechanical properties; other challenges relate to control over the attachment of molecules (e.g. antibodies, DNA) and cells on its surface, and to the addition of electronic function. The goal of this thesis is to develop paper as a substrate for a range of applications— microfluidics, substrates for electronic systems and MEMS, low-cost diagnostics, cell biology, and optics. The approach involves chemically modifying the surface of the paper to provide new functions without altering any of its defining properties: mechanical flexibility, foldability, light weight, gas permeability, and low cost. The first part of my thesis describes the modification of paper by silanization with organosilanes such as alkyl- and fluoroalkyl trichlorosilanes in the gas phase. Here, silanization is used to lower the surface free energy of the paper and to minimize the tendency of paper to absorb liquids and vapors, and especially water. Chapter 1 and Appendix 3 demonstrate that the combination of long fluoroalkyl chains of grafted siloxanes with the micro-scale roughness and porosity of paper yielded a material that is omniphobic (both hydrophobic and oleophobic), while preserving the properties of mechanical flexibility and low resistance to transport of gas of the untreated paper. Appendix 3 shows that features of omniphobic paper can be used to construct microtiter plates and liquid-filled gas sensors using standard paper folding techniques, while Appendix 4 shows that new type of microfluidic device fabricated by carving microchannels into the surface of omniphobic paper. The resulting devices have open, unobstructed channels (with dimensions as small as 45 μm) and thus exhibit fluid dynamics similar to conventional PDMS-based microfluidics, but are much lighter and have the potential to be much less expensive than PDMS-based devices. The second part of my thesis is focused on engineering the surface of paper to enable efficient immobilization of capture and target molecules for bioanalysis. In one approach, described in Appendix 5, we exploit the ease with which the surface chemistry of paper (i.e. the surface of the cellulose fibers making up the paper) can be modified, in order to enhance the immobilization of antibodies and antigens on the surface of the paper via hydrophobic interactions, while preventing the wicking of the fluids into the paper substrate. As an application in low-cost diagnostics, we describe a low-cost electrochemical device for ELISA intended for use in resource-limited settings. In a second approach, described in Chapter 2, we developed of an efficient procedure for assembling microarrays of ssDNA and proteins on paper, at the lowest practical cost. This method starts with the synthesis of DNA oligonucleotides covalently linked to paper, and proceeds to generate ssDNA arrays that, through hybridization with complementary strands of DNA, are capable of simultaneously capturing DNA, DNA-conjugated protein antigens, and DNA-conjugated antibodies. The third part of my thesis describes the simple, inexpensive fabrication of electrodes for paper-based electrochemical systems. A first method describes, in Appendix 6, the development of inkjet printing as a method for high resolution printing of conductive patterns on omniphobic “RF” paper, both to extend its promise as a substrate for paper electronics, and to enable us to integrate it into our program in low-cost, paper based diagnostics. A second method, described in Chapter 3, circumvents the need for printing, and instead focuses on the fabrication and reconfiguration of simple, versatile, and inexpensive electroanalytical devices in which conventional stainless-steel pins—in unmodified form or after coating with a carbon paste—are used as electrodes.Publication Paper-Based Electrical Respiration Sensor(Wiley-Blackwell, 2016) Guder, Firat; Ainla, Alar; Redston, Julia; Mosadegh, Bobak; Glavan, Ana; Martin, T. J.; Whitesides, GeorgeCurrent methods of monitoring breathing require cumbersome, inconvenient, and often expensive devices; this requirement sets practical limitations on the frequency and duration of measurements. This article describes a paper-based moisture sensor that uses the hygroscopic character of paper (i.e. the ability of paper to adsorb water reversibly from the surrounding environment) to measure patterns and rate of respiration by converting the changes in humidity caused by cycles of inhalation and exhalation to electrical signals. The changing level of humidity that occurs in a cycle causes a corresponding change in the ionic conductivity of the sensor, which can be measured electrically. By combining the paper sensor with conventional electronics, data concerning respiration can be transmitted to a nearby smartphone or tablet computer for post-processing, and subsequently to a cloud server. This means of sensing provides a new, practical method of recording and analyzing patterns of breathing.Publication Omniphobic “R F Paper” Produced by Silanization of Paper with Fluoroalkyltrichlorosilanes(Wiley-Blackwell, 2013) Glavan, Ana; Martinez, R; Subramaniam, Anand; Yoon, Hyo; Nunes, Rui M. D.; Lange, Heiko; Thuo, Martin M.; Whitesides, GeorgeThe fabrication and properties of “fluoroalkylated paper” (“\(R^F\) paper”) by vapor-phase silanization of paper with fluoroalkyl trichlorosilanes is reported. \(R^F\) paper is both hydrophobic and oleophobic: it repels water \((θ_{app}^{H2O} > 140^{\circ})\), organic liquids with surface tensions as low as \(28 \space mN \space m^{-1}\), aqueous solutions containing ionic and non-ionic surfactants, and complex liquids such as blood (which contains salts, surfactants, and biological material such as cells, proteins, and lipids). The propensity of the paper to resist wetting by liquids with a wide range of surface tensions correlates with the length and degree of fluorination of the organosilane (with a few exceptions in the case of methyl trichlorosilane-treated paper), and with the roughness of the paper. \(R^F\) paper maintains the high permeability to gases and mechanical flexibility of the untreated paper, and can be folded into functional shapes (e.g., microtiter plates and liquid-filled gas sensors). When impregnated with a perfluorinated oil, \(R^F\) paper forms a “slippery” surface (paper slippery liquid-infused porous surface, or “paper SLIPS“) capable of repelling liquids with surface tensions as low as \(15 \space mN \space m^{-1}\). The foldability of the paper SLIPS allows the fabrication of channels and flow switches to guide the transport of liquid droplets.Publication Soft Actuators and Robots that Are Resistant to Mechanical Damage(Wiley-Blackwell, 2014) Martinez, R; Glavan, Ana; Keplinger, Christoph; Oyetibo, Alexis I.; Whitesides, GeorgeThis paper characterizes the ability of soft pneumatic actuators and robots to resist mechanical insults that would irreversibly damage or destroy hard robotic systems—systems fabricated in metals and structural polymers, and actuated mechanically—of comparable sizes. The pneumatic networks that actuate these soft machines are formed by bonding two layers of elastomeric or polymeric materials that have different moduli on application of strain by pneumatic inflation; this difference in strain between an extensible top layer and an inextensible, strain-limiting, bottom layer causes the pneumatic network to expand anisotropically. While all the soft machines described here are, to some extent, more resistant to damage by compressive forces, blunt impacts, and severe bending than most corresponding hard systems, the composition of the strain-limiting layers confers on them very different tensile and compressive strengths.Publication Inkjet Printing of Conductive Inks with High Lateral Resolution on Omniphobic “R F Paper” for Paper-Based Electronics and MEMS(Wiley-Blackwell, 2014) Lessing, Joshua; Glavan, Ana; Walker, S. Brett; Keplinger, Christoph; Lewis, Jennifer; Whitesides, GeorgeThe use of omniphobic “fluoroalkylated paper” as a substrate for inkjet printing of aqueous inks that are the precursors of electrically conductive patterns is described. By controlling the surface chemistry of the paper, it is possible to print high resolution, conductive patterns that remain conductive after folding and exposure to common solvents.Publication Folding Analytical Devices for Electrochemical ELISA in Hydrophobic R H Paper(American Chemical Society (ACS), 2014) Glavan, Ana; Christodouleas, Dionysios; Mosadegh, Bobak; Yu, Hai Dong; Smith, Barbara S.; Lessing, Joshua; Fernández-Abedul, M. Teresa; Whitesides, GeorgeThis work describes a device for electrochemical enzyme-linked immunosorbent assay (ELISA) designed for low-resource settings and diagnostics at the point of care. The device is fabricated entirely in hydrophobic paper, produced by silanization of paper with decyl trichlorosilane, and comprises two zones separated by a central crease: an embossed microwell, on the surface of which the antigen or antibody immobilization and recognition events occur, and a detection zone where the electrodes are printed. The two zones are brought in contact by folding the device along this central crease; the analytical signal is recorded from the folded configuration. Two proof-of-concept applications, an electrochemical direct ELISA for the detection of rabbit IgG as a model antigen in buffer and an electrochemical sandwich ELISA for the detection of malarial histidine-rich protein from Plasmodium falciparum (Pf HRP2) in spiked human serum, show the versatility of this device. The limit of detection of the electrochemical sandwich ELISA for the quantification of Pf HRP2 in spiked human serum was 4 ng mL–1 (102 pmol L–1), a value within the range of clinically relevant concentrations.