Figure 2.6 ESI apparatus for offline analysis with microscope imaging.

MODELING AND CHARACTERIZATION OF MICROFABRICATED EMITTERS: IN PURSUIT OF IMPROVED ESI-MS PERFORMANCE

미세 가공 방사체의 모델링 및 특성화 : 개선된 ESI-MS 성능 추구

by XINYUN WU

A thesis submitted to the Department of Chemistry in conformity with the requirements for the degree of Master of Science Queen’s University Kingston, Ontario, Canada December, 2011 Copyright © Xinyun Wu, 2011

Abstract

ESI (Electrospray ionization)는 특히 탁월한 감도, 견고성 및 단순성으로 대형 생체 분자를 분석하는 데있어 질량 분석 (MS)에 매우 귀중한 기술이었습니다. ESI 기술 개발에 많은 노력을 기울였습니다. 그 형태와 기하학적 구조가 전기 분무 성능과 추가 MS 감지에 중추적 인 것으로 입증 되었기 때문입니다.

막힘 및 낮은 처리량을 포함하여 전통적인 단일 홀 이미터의 본질적인 문제는 기술의 적용 가능성을 제한합니다. 이 문제를 해결하기 위해 현재 프로젝트는 향상된 ESI-MS 분석을위한 다중 전자 분무(MES) 방출기를 개발하는데 초점을 맞추고 있습니다.

이 논문에서는 스프레이 전류 측정을 위한 전기 분무와 오프라인 전기 분무 실험을 위한 전산 유체 역학 (CFD) 시뮬레이션의 공동 작업이 수행되었습니다. 전기 분무 성능에 대한 다양한 이미터 설계의 영향을 테스트하기 위해 수치 시뮬레이션이 사용되었으며 실험실 결과는 가이드 및 검증으로 사용되었습니다.

CFD 코드는 Taylor-Melcher 누설 유전체 모델(LDM)을 기반으로 하며 과도 전기 분무 공정이 성공적으로 시뮬레이션되었습니다.

이 방법은 750 μm 내경 (i.d.) 이미 터를 통해 먼저 검증되었으며 20 μm i.d.에 추가로 적용되었습니다. 모델. 전기 분무 공정의 여러 단계가 시각적으로 시연되었으며 다양한 적용 전기장 및 유속에서 분무 전류의 변화에 ​​대한 정량적 조사는 이전 시뮬레이션 및 측정과 잘 일치합니다.

단일 조리개 프로토 타입을 기반으로 2 홀 및 3 홀 이미터로 MES 시뮬레이션을 수행했습니다. 시뮬레이션 예측은 실험 결과와 유사하게 비교되었습니다. 이 작업의 증거는 CFD 시뮬레이션이 MES의 이미 터 설계를 테스트하는 효과적인 수치 도구로 사용될 수 있음을 입증했습니다.

이 작업에서 달성 된 마이크로 스케일 에미 터 전기 분무의 성공적인 시뮬레이션에 대한 벤치마킹 결과는 현재까지 발표 된 전기 분무에 대한 동적 시뮬레이션의 가장 작은 규모로 여겨집니다.

Co-Authorship

공동 저자: 이 논문에 대한 모든 연구는 Natalie M. Cann 박사와 Richard D. Oleschuk 박사의 지도하에 완료되었습니다. 다중 전자 분무에 관한 4 장에서 제시된 연구 작업의 일부는 Ramin Wright가 공동 저술했으며, 이 작업은 press에서 다음 논문에서 인용되었습니다.

ibson,G.T.T.; Wright, R.D.; Oleschuk, R.D. Multiple electrosprays generated from a single poly carbonate microstructured fibre. Journal of Mass Spectrometry, 2011, in press.

Chapter 1 Introduction

소프트 이온화 방법으로 ESI (electrospray ionization)의 도입은 질량 분석법 (MS)의 적용 가능성에 혁명을 일으켰습니다. 이 기술의 부드러운 특징은 상대적으로 높은 전하를 가진 이온을 생성하는 고유한 이점으로 인해 액상에서 직접 펩티드 및 단백질과 같은 큰 생체 분자를 분석 할 수 있게했습니다 [1].

지난 10 년 동안 ESI-MS는 놀라운 성장을 보였으며 현재는 단백질 체학, 대사 체학, 글리코 믹스, 합성 화학자를 위한 식별 도구 등 다양한 생화학 분야에서 광범위하게 채택되고 있습니다 [2-3].

ESI-MS는 겔 전기 영동과 같은 생물학적 분자에 대한 기존의 질량 측정 기술보다 훨씬 빠르고 민감하며 정확합니다. 또한, 액체상에서 직접 분석 할 수 있는 큰 비 휘발성 분자의 능력은 고성능 액체 크로마토 그래피 (HPLC) 및 모세관 전기 영동 (CE)과 같은 업스트림 분리 기술과의 결합을 가능하게합니다 [4].

일반적인 ESI 공정은 일반적으로 액적 형성, 액적 수축 및 기상 이온의 최종 형성을 포함합니다. 일렉트로 스프레이의 성능에 영향을 미치는 많은 요소 중에서 스프레이를 위한 이미터의 구조 (즉, 기하학, 모양 등)가 중요한 요소입니다.

전통적인 전기 분무 이미터는 일반적으로 풀링 또는 에칭 기술로 제작 된 단일 채널 테이퍼 형 또는 비 테이퍼 형입니다. 그러나 이러한 이미터는 종종 막힘, 부적절한 처리량 등과 같은 문제로 어려움을 겪습니다. [5]

향상된 감도 및 샘플 활용을 위해 다중 스프레이를 생성하는 새로운 이미터 설계 개발로 분명한 발전이 있었습니다. 새로운 ESI 이미터 설계에 대한 연구는 실험적으로나 이론적으로 큰 관심을 불러 일으켰습니다 [3]. 그러나 ESI의 복잡한 물리적 과정은 팁 형상 외에도 많은 다른 변수에 의존하기 때문에 연구간 직접 비교의 어려움은 장애물이 됩니다.

또한 새로운 나노 이미터 제조 및 테스트 비용이 상당히 높을 수 있습니다. 이 논문은 CFD 시뮬레이션 도구를 활용하여 가상 랩을 설정함으로써 이러한 문제를 해결합니다. 다른 매개 변수로 인해 상호 연결된 변경 없이 다양한 이미터 설계를 비교할 수 있도록 이상적으로 균일한 물리적 조건을 제공합니다.

맞춤 제작된 프로토 타입의 실험 측정 값도 수집되어 더 나은 계산 체계를 형성하는 데 도움이 되는 지침과 검증을 모두 제공합니다. 특히 이 분야의 주요 미래 플랫폼으로 여겨지는 다중 노즐 이미 터 설계에 중점을 둘 것입니다.

전기 분무 거동에 영향을 미치는 요인에 대한 추가 기본 연구는 다양한 기하학적 및 작동 매개 변수와 관련하여 수행됩니다. 이는 보다 효율적이고 견고한 이미터의 개발을 가능하게 할 뿐만 아니라 더 넓은 영역에서 ESI의 적용을 향상시킬 수 있습니다.

Figure 1.1Schematic setup for ESI-MS technique
Figure 1.1Schematic setup for ESI-MS technique
Figure 1.2 Schematic of major processes occurring in electrospray [5].
Figure 1.2 Schematic of major processes occurring in electrospray [5].
Figure 1.3 Illustration of detailed geometric parameters of a spraying Taylor cone wherera is the radius of curvature of the best fitting circle at the tip of the cone; re is the radius of the emission region for droplets at the tip of a Taylor cone;is the liquid cone angle.
Figure 1.3 Illustration of detailed geometric parameters of a spraying Taylor cone wherera is the radius of curvature of the best fitting circle at the tip of the cone; re is the radius of the emission region for droplets at the tip of a Taylor cone;is the liquid cone angle.
Figure 1.4 (A)Externally tapered emitter (B) Optical image of a clogged tapered emitter with normal use [46].
Figure 1.4 (A)Externally tapered emitter (B) Optical image of a clogged tapered emitter with normal use [46].
Figure 1.5 (A)Three by three configuration of an emitter array made with polycarbonate using laser ablation; (B) Photomicrograph of nine stable electrosprays generated from the nine-emitter array [52]
Figure 1.5 (A)Three by three configuration of an emitter array made with polycarbonate using laser ablation; (B) Photomicrograph of nine stable electrosprays generated from the nine-emitter array [52]
Figure 1.6 SEM images of the distal ends of four multichannel nanoelectrospray emitters and a tapered emitter: (A) 30 orifice emitter; (B) 54 orifice emitter; (C) 84 orifice emitter; (D) 168 orifice emitter; Scale bars in A, B, and C represent 50 μm, and 100 μm in D[54]
Figure 1.6 SEM images of the distal ends of four multichannel nanoelectrospray emitters and a tapered emitter: (A) 30 orifice emitter; (B) 54 orifice emitter; (C) 84 orifice emitter; (D) 168 orifice emitter; Scale bars in A, B, and C represent 50 μm, and 100 μm in D[54]
Figure 1.7 Photomicrographs of electrospray from of a 168-hole MCN emitter at different flow rates. (A) A traditional integrated Taylor cone observed from offline electrospray of water with 0.1% formic acid at 300 nL/min; (B) A mist of coalesced Taylor cones observed from offline electrospray at 25 nL/min[54]
Figure 1.7 Photomicrographs of electrospray from of a 168-hole MCN emitter at different flow rates. (A) A traditional integrated Taylor cone observed from offline electrospray of water with 0.1% formic acid at 300 nL/min; (B) A mist of coalesced Taylor cones observed from offline electrospray at 25 nL/min[54]
Figure 1.8 Circular arrays of etched emitters for better electric field homogeneity [53].
Figure 1.8 Circular arrays of etched emitters for better electric field homogeneity [53].
Figure 2.6 ESI apparatus for offline analysis with microscope imaging.
Figure 2.6 ESI apparatus for offline analysis with microscope imaging.
Figure 3.9 Typical panel for displaying instant simulation result during simulation process.
Figure 3.9 Typical panel for displaying instant simulation result during simulation process.
Figure 5.3 Generation of a Taylor cone-jet mode (simulation) plotted with iso-potential lines at times (Top to bottom panels correspond to 0.002 s, 0.012 s, 0.018 s, 0.08 s respectively).
Figure 5.3 Generation of a Taylor cone-jet mode (simulation) plotted with iso-potential lines at times (Top to bottom panels correspond to 0.002 s, 0.012 s, 0.018 s, 0.08 s respectively).
Figure 5.8 (A) Taylor cone-jet profiles with different contact angle of 30 degrees and 20 degrees (B) under the same physical conditions of 6 kV and 0.04 m/s. (C) Cone-jet profile generated from a tapered tip with a 20 degree contact angle at 6 kV and 0.04 m/s (as a comparison with (B)).
Figure 5.8 (A) Taylor cone-jet profiles with different contact angle of 30 degrees and 20 degrees (B) under the same physical conditions of 6 kV and 0.04 m/s. (C) Cone-jet profile generated from a tapered tip with a 20 degree contact angle at 6 kV and 0.04 m/s (as a comparison with (B)).

Omit below: Please refer to the original text for the full content.

Bibliography

1. Mclafferty, F.W., Tandem Fourier-Transform Mass-Spectrometry of Large Molecules.Abstracts of Papers of the American Chemical Society, 1986. 192: p. 21-Anyl. 2. Griffiths, W.J. and Y.Q. Wang, Mass spectrometry: from proteomics to metabolomics and lipidomics. Chemical Society Reviews, 2009. 38(7): p. 1882-1896. 3. Gibson, G.T.T., S.M. Mugo, and R.D. Oleschuk, Nanoelectrospray Emitters: Trends and Perspective. Mass Spectrometry Reviews, 2009. 28(6): p. 918-936. 4. Cech, N.B. and C.G. Enke, Practical implications of some recent studies in electrospray ionization fundamentals. Mass Spectrometry Reviews, 2001. 20(6): p. 362-387. 5. Su, S., Development and Application of Non-tapered Electrospray Emitters for Nano-ESI Mass Spectrometry, in Chemistry. 2008, Queen’s University: Kingston. p. 185. 6. Zeleny, J., The electrical discharge from liquid points, and a hydrostatic method of measuring the electric intensity at their surfaces. Physical Review, 1914. 3(2): p. 69-91. 7. Dole, M., L.L. Mack, and R.L. Hines, Molecular Beams of Macroions. Journal of Chemical Physics, 1968. 49(5): p. 2240-&. 8. Yamashita, M. and J.B. Fenn, Negative-Ion Production with the Electrospray Ion-Source.Journal of Physical Chemistry, 1984. 88(20): p. 4671-4675. 9. Kebarle, P. and U.H. Verkerk, Electrospray: From Ions in Solution to Ions in the Gas Phase, What We Know Now. Mass Spectrometry Reviews, 2009. 28(6): p. 898-917. 10. Taylor, G., Disintegration of Water Drops in Electric Field. Proceedings of the Royal Society of London Series a-Mathematical and Physical Sciences, 1964. 280(138): p. 383. 11. Cole, R.B., Some tenets pertaining to electrospray ionization mass spectrometry. Journal of Mass Spectrometry, 2000. 35(7): p. 763-772. 12. Rayleigh, L., On the equilibrium of liquid conducting masses charged with electricity.Philos. Mag., 1882. 14: p. 184-186. 13. Mack, L.L., et al., Molecular Beams of Macroions .2. Journal of Chemical Physics, 1970. 52(10): p. 4977-&. 14. Gamero-Castano, M. and J.F. de la Mora, Kinetics of small ion evaporation from the charge and mass distribution of multiply charged clusters in electrosprays. Journal of Mass Spectrometry, 2000. 35(7): p. 790-803. 15. Gamero-Castano, M. and J.F. de la Mora, Modulations in the abundance of salt clusters in electrosprays. Analytical Chemistry, 2000. 72(7): p. 1426-1429. 16. Loscertales, I.G. and J.F. Delamora, Experiments on the Kinetics of Field Evaporation of Small Ions from Droplets. Journal of Chemical Physics, 1995. 103(12): p. 5041-5060. 17. Rohner, T.C., N. Lion, and H.H. Girault, Electrochemical and theoretical aspects of electrospray ionisation. Physical Chemistry Chemical Physics, 2004. 6(12): p. 3056-3068.

18. Iribarne, J.V. and B.A. Thomson, Evaporation of Small Ions from Charged Droplets.Journal of Chemical Physics, 1976. 64(6): p. 2287-2294. 19. Meng, C.K. and J.B. Fenn, Formation of Charged Clusters during Electrospray Ionization of Organic Solute Species. Organic Mass Spectrometry, 1991. 26(6): p. 542-549. 20. Nohmi, T. and J.B. Fenn, Electrospray Mass-Spectrometry of Poly(Ethylene Glycols) with Molecular-Weights up to 5 Million. Journal of the American Chemical Society, 1992. 114(9): p. 3241-3246. 21. de la Mora, J.F., Electrospray ionization of large multiply charged species proceeds via Dole’s charged residue mechanism. Analytica Chimica Acta, 2000. 406(1): p. 93-104. 22. Iavarone, A.T., J.C. Jurchen, and E.R. Williams, Supercharged protein and peptide lone formed by electrospray ionization. Analytical Chemistry, 2001. 73(7): p. 1455-1460. 23. Hogan, C.J., et al., Charge carrier field emission determines the number of charges on native state proteins in electrospray ionization. Journal of the American Chemical Society, 2008. 130(22): p. 6926-+. 24. Nguyen, S. and J.B. Fenn, Gas-phase ions of solute species from charged droplets of solutions. Proceedings of the National Academy of Sciences of the United States of America, 2007. 104(4): p. 1111-1117. 25. Luedtke, W.D., et al., Nanojets, electrospray, and ion field evaporation: Molecular dynamics simulations and laboratory experiments. Journal of Physical Chemistry A, 2008. 112(40): p. 9628-9649. 26. Enke, C.G., A predictive model for matrix and analyte effects in electrospray ionization of singly-charged ionic analytes. Analytical Chemistry, 1997. 69(23): p. 4885-4893. 27. Maze, J.T., T.C. Jones, and M.F. Jarrold, Negative droplets from positive electrospray.Journal of Physical Chemistry A, 2006. 110(46): p. 12607-12612. 28. Kebarle, P. and M. Peschke, On the mechanisms by which the charged droplets produced by electrospray lead to gas phase ions. Analytica Chimica Acta, 2000. 406(1): p. 11-35. 29. Loeb, L.B., A.F. Kip, and G.G. Hudson, Pulses in negative point-to-plane corona.Physical Review, 1941. 60(10): p. 714-722. 30. Cole, R.B., Electrospray ionization mass spectrometry : fundamentals, instrumentation, and applications. 1997, New York: Wiley. xix, 577 p. 31. Smith, D.P.H., The Electrohydrodynamic Atomization of Liquids. Ieee Transactions on Industry Applications, 1986. 22(3): p. 527-535. 32. Taylor, G.I. and A.D. Mcewan, Stability of a Horizontal Fluid Interface in a Vertical Electric Field. Journal of Fluid Mechanics, 1965. 22: p. 1-&. 33. Ikonomou, M.G., A.T. Blades, and P. Kebarle, Electrospray Mass-Spectrometry of Methanol and Water Solutions Suppression of Electric-Discharge with Sf6 Gas. Journal of the American Society for Mass Spectrometry, 1991. 2(6): p. 497-505.

34. Wampler, F.M., A.T. Blades, and P. Kebarle, Negative-Ion Electrospray Mass-Spectrometry of Nucleotides – Ionization from Water Solution with Sf6 Discharge Suppression. Journal of the American Society for Mass Spectrometry, 1993. 4(4): p. 289-295. 35. Marginean, I., P. Nemes, and A. Vertes, Order-chaos-order transitions in electrosprays: The electrified dripping faucet. Physical Review Letters, 2006. 97(6): p. -. 36. Marginean, I., P. Nemes, and A. Vertes, Astable regime in electrosprays. Physical Review E, 2007. 76(2): p. -. 37. Nemes, P., I. Marginean, and A. Vertes, Spraying mode effect on droplet formation and ion chemistry in electrosprays. Analytical Chemistry, 2007. 79(8): p. 3105-3116. 38. Marginean, I., et al., Electrospray characteristic curves: In pursuit of improved performance in the nanoflow regime. Analytical Chemistry, 2007. 79(21): p. 8030-8036. 39. Page, J.S., et al., Subambient pressure ionization with nanoelectrospray source and interface for improved sensitivity in mass spectrometry. Analytical Chemistry, 2008. 80(5): p. 1800-1805. 40. Delamora, J.F. and I.G. Loscertales, The Current Emitted by Highly Conducting Taylor Cones. Journal of Fluid Mechanics, 1994. 260: p. 155-184. 41. Ganan-Calvo, A.M., On the general scaling theory for electrospraying. Journal of Fluid Mechanics, 2004. 507: p. 203-212. 42. Smith, D.R., G. Sagerman, and T.D. Wood, Design and development of an interchangeable nanomicroelectrospray source for a quadrupole mass spectrometer.Review of Scientific Instruments, 2003. 74(10): p. 4474-4477. 43. Barnidge, D.R., S. Nilsson, and K.E. Markides, A design for low-flow sheathless electrospray emitters. Analytical Chemistry, 1999. 71(19): p. 4115-4118. 44. Guzzetta, A.W., R.A. Thakur, and I.C. Mylchreest, A robust micro-electrospray ionization technique for high-throughput liquid chromatography/mass spectrometry proteomics using a sanded metal needle as an emitter. Rapid Communications in Mass Spectrometry, 2002. 16(21): p. 2067-2072. 45. Wilm, M. and M. Mann, Analytical properties of the nanoelectrospray ion source.Analytical Chemistry, 1996. 68(1): p. 1-8. 46. Covey, T.R. and D. Pinto, Practical Spectroscopy. Vol. 32. 2002. 47. Kelly, R.T., et al., Nanoelectrospray emitter arrays providing interemitter electric field uniformity. Analytical Chemistry, 2008. 80(14): p. 5660-5665. 48. Choi, Y.S. and T.D. Wood, Polyaniline-coated nanoelectrospray emitters treated with hydrophobic polymers at the tip. Rapid Communications in Mass Spectrometry, 2007. 21(13): p. 2101-2108. 49. Tojo, H., Properties of an electrospray emitter coated with material of low surface energy. Journal of Chromatography A, 2004. 1056(1-2): p. 223-228.

50. Liu, J., et al., Electrospray ionization with a pointed carbon fiber emitter. Analytical Chemistry, 2004. 76(13): p. 3599-3606. 51. Sen, A.K., et al., Modeling and characterization of a carbon fiber emitter for electrospray ionization. Journal of Micromechanics and Microengineering, 2006. 16(3): p. 620-630. 52. Tang, K.Q., et al., Generation of multiple electrosprays using microfabricated emitter arrays for improved mass spectrometric sensitivity. Analytical Chemistry, 2001. 73(8): p. 1658-1663. 53. Deng, W. and A. Gomez, Influence of space charge on the scale-up of multiplexed electrosprays. Journal of Aerosol Science, 2007. 38(10): p. 1062-1078. 54. Su, S.Q., et al., Microstructured Photonic Fibers as Multichannel Electrospray Emitters.Analytical Chemistry, 2009. 81(17): p. 7281-7287. 55. Sen, A.K., J. Darabi, and D.R. Knapp, Simulation and parametric study of a novel multi-spray emitter for ESI-MS applications. Microfluidics and Nanofluidics, 2007. 3(3): p. 283-298. 56. Hayati, I., A. Bailey, and T.F. Tadros, Investigations into the Mechanism of Electrohydrodynamic Spraying of Liquids .2. Mechanism of Stable Jet Formation and Electrical Forces Acting on a Liquid Cone. Journal of Colloid and Interface Science, 1987. 117(1): p. 222-230. 57. Glonti, G.A., On the Theory of the Stability of Liquid Jets in an Electric Field. Soviet Physics Jetp-Ussr, 1958. 7(5): p. 917-918. 58. Nayyar, N.K. and G.S. Murty, The Stability of a Dielectric Liquid Jet in the Presence of a Longitudinal Electric Field. Proceedings of the Physical Society of London, 1960. 75(483): p. 369-373. 59. Allan, R.S. and S.G. Mason, Particle Behaviour in Shear and Electric Fields .1. Deformation and Burst of Fluid Drops. Proceedings of the Royal Society of London Series a-Mathematical and Physical Sciences, 1962. 267(1328): p. 45-&. 60. Melcher, J.R. and G.I. Taylor, Electrohydrodynamics – a Review of Role of Interfacial Shear Stresses. Annual Review of Fluid Mechanics, 1969. 1: p. 111-&. 61. Saville, D.A., Electrohydrodynamics: The Taylor-Melcher leaky dielectric model. Annual Review of Fluid Mechanics, 1997. 29: p. 27-64. 62. Carretero Benignos, J.A. and Massachusetts Institute of Technology. Dept. of Mechanical Engineering., Numerical simulation of a single emitter colloid thruster in pure droplet cone-jet mode. 2005. p. 117 leaves. 63. Hartman, R.P.A., et al., The evolution of electrohydrodynamic sprays produced in the cone-jet mode, a physical model. Journal of Electrostatics, 1999. 47(3): p. 143-170. 64. Hartman, R.P.A., et al., Electrohydrodynamic atomization in the cone-jet mode physical modeling of the liquid cone and jet. Journal of Aerosol Science, 1999. 30(7): p. 823-849.

65. Yoon, S.S., et al., Modeling multi-jet mode electrostatic atomization using boundary element methods. Journal of Electrostatics, 2001. 50(2): p. 91-108. 66. Zeng, J., D. Sobek, and T. Korsmeyer, Electro-hydrodynamic modeling of electrospray ionization: Cad for a mu fluidic device – Mass spectrometer interface. Boston Transducers’03: Digest of Technical Papers, Vols 1 and 2, 2003: p. 1275-1278, 1938. 67. Lastow, O. and W. Balachandran, Numerical simulation of electrohydrodynamic (EHD) atomization. Journal of Electrostatics, 2006. 64(12): p. 850-859. 68. http://www.flow3d.com. 69. Valaskovic, G.A., et al., Attomole-Sensitivity Electrospray Source for Large-Molecule Mass-Spectrometry. Analytical Chemistry, 1995. 67(20): p. 3802-3805. 70. Kriger, M.S., K.D. Cook, and R.S. Ramsey, Durable Gold-Coated Fused-Silica Capillaries for Use in Electrospray Mass-Spectrometry. Analytical Chemistry, 1995. 67(2): p. 385-389. 71. Fang, L.L., et al., Online Time-of-Flight Mass-Spectrometric Analysis of Peptides Separated by Capillary Electrophoresis. Analytical Chemistry, 1994. 66(21): p. 3696-3701. 72. Cao, P. and M. Moini, A novel sheathless interface for capillary electrophoresis/electrospray ionization mass spectrometry using an in-capillary electrode. Journal of the American Society for Mass Spectrometry, 1997. 8(5): p. 561-564. 73. Fong, K.W.Y. and T.W.D. Chan, A novel nonmetallized tip for electrospray mass spectrometry at nanoliter flow rate. Journal of the American Society for Mass Spectrometry, 1999. 10(1): p. 72-75. 74. Emmett, M.R. and R.M. Caprioli, Micro-Electrospray Mass-Spectrometry – Ultra-High-Sensitivity Analysis of Peptides and Proteins. Journal of the American Society for Mass Spectrometry, 1994. 5(7): p. 605-613. 75. Gatlin, C.L., et al., Protein identification at the low femtomole level from silver-stained gels using a new fritless electrospray interface for liquid chromatography microspray and nanospray mass spectrometry. Analytical Biochemistry, 1998. 263(1): p. 93-101. 76. Aturki, Z., et al., On-line CE-MS using pressurized liquid junction nanoflow electrospray interface and surface-coated capillaries. Electrophoresis, 2006. 27(23): p. 4666-4673. 77. Edwards, J.L., et al., Negative mode sheathless capillary electrophoresis electrospray ionization-mass spectrometry for metabolite analysis of prokaryotes. Journal of Chromatography A, 2006. 1106(1-2): p. 80-88. 78. http://www.kiriama.com/kiriama%20single-mode%20polymer%20fibers_009.htm. 79. Wilm, M.S. and M. Mann, Electrospray and Taylor-Cone Theory, Doles Beam of Macromolecules at Last. International Journal of Mass Spectrometry, 1994. 136(2-3): p. 167-180.

80. Hirt, C.W. and B.D. Nichols, Volume of Fluid (Vof) Method for the Dynamics of Free Boundaries. Journal of Computational Physics, 1981. 39(1): p. 201-225. 81. Melcher, J.R., Continuum electromechanics. 1981, Cambridge, Mass.: MIT Press. 1 v. (various pagings). 82. http://www.flow3d.com/cfd-101/cfd-101-FAVOR.html. 83. http://www.flow3d.com/cfd-101/cfd-101-FAVOR-no-loss.html. 84. Savage, B.M. and M.C. Johnson, Flow over ogee spillway: Physical and numerical model case study. Journal of Hydraulic Engineering-Asce, 2001. 127(8): p. 640-649. 85. http://www.flow3d.com/cfd-101/cfd-101-free-surface-fluid-flow.html. 86. Graham T. T. Gibson, R.D.W.a.R.D.O., Multiple electrosprays generated from a single poly carbonate microstructured fibre. Mass Spectrometry, 2011. 87. Smith, R.D., et al., Analytical characterization of the electrospray ion source in the nanoflow regime. Analytical Chemistry, 2008. 80(17): p. 6573-6579. 88. Hirt, C.W., Electro-hydrodynamics of semi-conductive fluids: with application to electro-spraying. Flow Science Technical Note, 2004. 70(FSI–04–TN70): p. 1-7. 89. de la Mora, J.F., The fluid dynamics of Taylor cones. Annual Review of Fluid Mechanics, 2007. 39: p. 217-243. 90. Cloupeau, M. and B. Prunetfoch, Electrostatic Spraying of Liquids in Cone-Jet Mode.Journal of Electrostatics, 1989. 22(2): p. 135-159. 91. Hayati, I., A.I. Bailey, and T.F. Tadros, Investigations into the Mechanisms of Electrohydrodynamic Spraying of Liquids .1. Effect of Electric-Field and the Environment on Pendant Drops and Factors Affecting the Formation of Stable Jets and Atomization. Journal of Colloid and Interface Science, 1987. 117(1): p. 205-221. 92. FLOW-3D User Manual, Ver. 9.4. 93. Sen, A.K., J. Darabi, and D.R. Knapp, Analysis of Droplet Generation in Electrospray Using a Carbon Fiber Based Microfluidic Emitter. Journal of Fluids Engineering-Transactions of the Asme, 2011. 133(7).

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Figure 2. Simulation of droplet separation by EWOD

Non-Linear Electrohydrodynamics in Microfluidic Devices

미세 유체 장치의 비선형 전기 유체 역학

by Jun ZengHewlett-Packard Laboratories, Hewlett-Packard Company, 1501 Page Mill Road, Palo Alto, CA 94304, USAInt. J. Mol. Sci.2011, 12(3), 1633-1649; https://doi.org/10.3390/ijms12031633Received: 24 January 2011 / Revised: 10 February 2011 / Accepted: 24 February 2011 / Published: 3 March 2011

Abstract

Since the inception of microfluidics, the electric force has been exploited as one of the leading mechanisms for driving and controlling the movement of the operating fluid and the charged suspensions. Electric force has an intrinsic advantage in miniaturized devices. Because the electrodes are placed over a small distance, from sub-millimeter to a few microns, a very high electric field is easy to obtain. The electric force can be highly localized as its strength rapidly decays away from the peak. This makes the electric force an ideal candidate for precise spatial control. The geometry and placement of the electrodes can be used to design electric fields of varying distributions, which can be readily realized by Micro-Electro-Mechanical Systems (MEMS) fabrication methods. In this paper, we examine several electrically driven liquid handling operations. The emphasis is given to non-linear electrohydrodynamic effects. We discuss the theoretical treatment and related numerical methods. Modeling and simulations are used to unveil the associated electrohydrodynamic phenomena. The modeling based investigation is interwoven with examples of microfluidic devices to illustrate the applications. 

Keywords: dielectrophoresis; electrohydrodynamics; electrowetting; lab-on-a-chip; microfluidics; modeling; numerical simulation; reflective display

요약

미세 유체학이 시작된 이래로 전기력은 작동 유체와 충전 된 서스펜션의 움직임을 제어하고 제어하는 ​​주요 메커니즘 중 하나로 활용되어 왔습니다. 전기력은 소형 장치에서 본질적인 이점이 있습니다. 전극이 밀리미터 미만에서 수 미크론까지 작은 거리에 배치되기 때문에 매우 높은 전기장을 쉽게 얻을 수 있습니다. 

전기력은 강도가 피크에서 멀어지면서 빠르게 감소하기 때문에 고도로 국부화 될 수 있습니다. 이것은 전기력을 정밀한 공간 제어를 위한 이상적인 후보로 만듭니다.

전극의 기하학적 구조와 배치는 다양한 분포의 전기장을 설계하는 데 사용될 수 있으며, 이는 MEMS (Micro-Electro-Mechanical Systems) 제조 방법으로 쉽게 실현할 수 있습니다. 

이 논문에서 우리는 몇 가지 전기 구동 액체 처리 작업을 검토합니다. 비선형 전기 유체 역학적 효과에 중점을 둡니다. 이론적 처리 및 관련 수치 방법에 대해 논의합니다. 모델링과 시뮬레이션은 관련된 전기 유체 역학 현상을 밝히는 데 사용됩니다. 모델링 기반 조사는 응용 분야를 설명하기 위해 미세 유체 장치의 예와 결합됩니다. 

키워드 : 유전 영동 ; 전기 유체 역학 ; 전기 습윤 ; 랩 온어 칩 ; 미세 유체 ; 모델링 ; 수치 시뮬레이션 ; 반사 디스플레이

Droplet processing array Droplet based BioFlip
igure 1. Example of droplet-based digital microfluidics architecture. Above is an elevation view showing the layered structure of the chip. Below is a diagram illustrating the system (Adapted from [4]).
Figure 2. Simulation of droplet separation by EWOD
Figure 2. Simulation of droplet separation by EWOD. The top two figures illustrate the device configuration. Electric voltages are applied to all four electrodes embedded in the insulating material. The bottom left figure shows transient simulation solution. It illustrates the process of separating one droplet into two via EWOD. The bottom right figure shows the electric potential distribution inside the device. The color indicates the electric potential; the iso-potential surfaces are also drawn. The image shows the electric field is absent within the droplet body indicating the droplet is either conductive or highly polarizable.
Figure 4. Transient sequence of the Taylor cone formation
Figure 4. Transient sequence of the Taylor cone formation: simulation and experiment comparison. Experimental images are shown in the top row. Simulation results are shown in the bottom row. Their correspondence is indicated by the vertical alignment (Adapted from [4]).
Figure 6. Simulation of charge screening effect using a parallel-plate cell
Figure 6. Simulation of charge screening effect using a parallel-plate cell. Top-left image shows the electric current as function of time and driving voltage, top-right image shows the evolution of the species concentration as function of time and space, the bottom image shows the electric current readout after switching the applied voltage.
Figure 7. Transient simulation of electrohydrodynamic instability and the development of the cellular convective flow pattern.
Figure 7. Transient simulation of electrohydrodynamic instability and the development of the cellular convective flow pattern.
Figure 3. Simulation of dielectrophoresis driven axon migration
Figure 3. Simulation of dielectrophoresis driven axon migration. The set of small images on the left shows a transient simulation of single axon migration under an electric field generated by a pin electrode. The image on the right is a snapshot of a simulation where two axons are fused by dielectrophoresis using a pin electrode. Axons are outlined in white. Also shown are the iso-potential curves.
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References

  1. Muller, RS. MEMS: Quo vadis in century XXI. Microelectron. Eng 2000, 53(1–4), 47–54. [Google Scholar]
  2. Reyes, DR; Iossifidis, D; Auroux, PA; Manz, A. Micro total analysis systems. 1. Introduction, theory, and technology. Anal.Chem 2002, 74, 2623–2636. [Google Scholar]
  3. Levy, U; Shamai, R. Tunable optofluidic devices. Microfluid. Nanofluid 2008, 4, 97–105. [Google Scholar]
  4. Zeng, J; Korsmeyer, FT. Principles of droplet electrohydrodynamics for lab-on-a-chip. Lab Chip 2004, 4, 265–277. [Google Scholar]
  5. Fair, RB. Digital microfluidics: Is a true lab-on-a-chip possible? Microfluid. Nanofluid 2007, 3, 245–281. [Google Scholar]
  6. Pollack, MG; Fair, RB; Shenderov, AD. Electrowetting-based actuation of liquid droplets for microfluidic applications. Appl. Phys. Lett 2000, 77(11), 1725–1726. [Google Scholar]
  7. Peykov, V; Quinn, A; Ralston, J. Electrowetting: A model for contact-angle saturation. Colloid Polym. Sci 2000, 278, 789–793. [Google Scholar]
  8. Verheijen, HJJ; Prins, MWJ. Reversible electrowetting and trapping of charge: Model and experiments. Langmuir 1999, 15, 6616–6620. [Google Scholar]
  9. Mugele, F; Baret, J. Electrowetting: From basics to applications. J. Phys. Condens. Matter 2005, 17, R705–R774. [Google Scholar]
  10. Quilliet, C; Berge, B. Electrowetting: A recent outbreak. Curr. Opin. Colloid Interface Sci 2001, 6, 34–39. [Google Scholar]
  11. Probstein, RF. Physicochemical Hydrodynamics; Wiley: New York, NY, USA, 1994. [Google Scholar]
  12. Koo, J; Kleinstreuer, C. Liquid flow in microchannels: Experimental observations and computational analyses of microfluidics effects. J. Micromech. Microeng 2003, 13, 568–579. [Google Scholar]
  13. Hu, G; Li, D. Multiscale phenomena in microfluidics and nanofluidics. Chem. Eng. Sci 2007, 62, 3443–3454. [Google Scholar]
  14. Haus, HA; Melcher, JR. Electromagnetic Fields and Energy; Prentice-Hall: Englewood Cliffs, NJ, USA, 1989. [Google Scholar]
  15. Leal, LG. Laminar Flow and Convective Transport Processes: Scaling Principles and Asymptotic Analysis; Butterworth-Heinemann: Oxford, UK, 1992. [Google Scholar]
  16. Collins, RT; Harris, MT; Basaran, OA. Breakup of electrified jets. J. Fluid Mech 2007, 588, 75–129. [Google Scholar]
  17. Sista, R; Hua, Z; Thwar, P; Sudarsan, A; Srinivasan, V; Eckhardt, A; Pollack, M; Pamula, V. Development of a digital microfluidic platform for point of care testing. Lab Chip 2008, 8, 2091–2104. [Google Scholar]
  18. Zeng, J. Modeling and simulation of electrified droplets and its application to computer-aided design of digital microfluidics. IEEE Trans. Comput. Aid. Des. Integr. Circ. Syst 2006, 25(2), 224–233. [Google Scholar]
  19. Walker, SW; Bonito, A; Nochetto, RH. Mixed finite element method for electrowetting on dielectric with contact line pinning. Interface. Free Bound 2010, 12, 85–119. [Google Scholar]
  20. Eck, C; Fontelos, M; Grün, G; Klingbeil, F; Vantzos, O. On a phase-field model for electrowetting. Interface. Free Bound 2009, 11, 259–290. [Google Scholar]
  21. Gascoyne, PRC; Vykoukal, JV. Dielectrophoresis-based sample handling in general-purpose programmable diagnostic instruments. Proc. IEEE 2004, 92(1), 22–42. [Google Scholar]
  22. Jones, TB; Gunji, M; Washizu, M. Dielectrophoretic liquid actuation and nanodroplet formation. J. Appl. Phys 2001, 89(3), 1441–1448. [Google Scholar]
  23. Sretavan, D; Chang, W; Keller, C; Kliot, M. Microscale surgery on single axons. Neurosurgery 2005, 57(4), 635–646. [Google Scholar]
  24. Pohl, HA; Crane, JS. Dielectrophoresis of cells. Biophys. J 1971, 11, 711–727. [Google Scholar]
  25. Melcher, JR; Taylor, GI. Electrohydrodynamics: A review of the role of interfacial shear stresses. Annu. Rev. Fluid Mech 1969, 1, 111–146. [Google Scholar]
  26. Saville, DA. Electrohydrodynamics: The taylor-melcher leaky-dielectric model. Annu. Rev. Fluid Mech 1997, 29, 27–64. [Google Scholar]
  27. Schultz, GA; Corso, TN; Prosser, SJ; Zhang, S. A fully integrated monolithic microchip electrospray device for mass spectrometry. Anal. Chem 2000, 72(17), 4058–4063. [Google Scholar]
  28. Killeen, K; Yin, H; Udiavar, S; Brennen, R; Juanitas, M; Poon, E; Sobek, D; van de Goor, T. Chip-MS: A polymeric microfluidic device with integrated mass-spectrometer interface. Micro Total Anal. Syst 2001, 331–332. [Google Scholar]
  29. Dukhin, SS. Electrokinetic phenomena of the second kind and their applications. Adv. Colloid Interface Sci 1991, 35, 173–196. [Google Scholar]
  30. Wang, Y-C; Stevens, AL; Han, J. Million-fold preconcentration of proteins and peptides by nanofluidic filter. Anal. Chem 2005, 77(14), 4293–4299. [Google Scholar]
  31. Kim, SJ; Wang, Y-C; Han, J. Nonlinear electrokinetic flow pattern near nanofluidic channel. Micro Total Anal. Syst 2006, 1, 522–524. [Google Scholar]
  32. Comiskey, B; Albert, JD; Yoshizawa, H; Jacobson, J. An electrophoretic ink for all-printed reflective electronic displays. Nature 1998, 394(6690), 253–255. [Google Scholar]
  33. Beunis, F; Strubbe, F; Neyts, K; Bert, T; De Smet, H; Verschueren, A; Schlangen, L. P-39: Electric field compensation in electrophoretic ink display. In Proceedings of the Twenty-fifth International Display Research Conference—Eurodisplay 2005; Edinburgh, UK, 19–22 2005; pp. 344–345. [Google Scholar]
  34. Strubbe, F; Verschueren, ARM; Schlangen, LJM; Beunis, F; Neyts, K. Generation current of charged micelles in nonaqueous liquids: Measurements and simulations. J. Colloid Interface Sci 2006, 300, 396–403. [Google Scholar]
  35. Hsu, MF; Dufresne, ER; Weitz, DA. Charge stabilization in nonpolar solvents. Langmuir 2005, 21, 4881–4887. [Google Scholar]
  36. Hayes, RA; Feenstra, BJ. Video-speed electronic paper based on electrowetting. Nature 2003, 425, 383–385. [Google Scholar]
  37. Chakrabarty, K; Su, F. Digital Microfluidic Biochips: Synthesis, Testing, and Reconfiguration Techniques; CRC Press: Boca Raton, FL, USA, 2006. [Google Scholar]
  38. Chakrabarty, K; Fair, RB; Zeng, J. Design tools for digital microfluidic biochips: Towards functional diversification and more than Moore. IEEE Trans.CAD Integr. Circ. Syst 2010, 29(7), 1001–1017. [Google Scholar]

Electro-Hydrodynamics of Semi-Conductive Fluids With Application to Electro-Spraying

Background
It has long been known that strong electric fields can disrupt liquid surfaces. One particularly useful application of this observation has been the development of electrospray-ionization (ESI) systems.

The basic concept is to eject liquid from a nozzle connected to a voltage source that has a relatively high electric potential compared to its surroundings. When adjusted for certain operating conditions, a thin jet of liquid is ejected from the nozzle that subsequently breaks up into charged droplets having a relatively uniform size. There are many useful industrial applications for a system that produces small droplets of specified size; particularly if the droplets don’t coalesce because of their electrical repulsion.

Having a charge also means that these drops can be electrically deflected toward a target. This technology, for example, has been advantageously applied to paint spraying, atomization of fuels, printing, mass spectroscopy and a variety of spray drying processes.

Addition of Dielectric Phenomena to FLOW-3D

Overview
There are situations where it would be helpful to account for the interaction of electric fields with liquid and solid materials. For example, electrostatic air cleaners rely on the ability to attract small particles in flowing air to a surface where they can be collected and removed from the air. In this case the primary attractive force arises from dielectric polarization of the particles.
Spraying liquid drops onto a surface, as in spray painting, is often improved by electrifying the drops so that they repel one another and produce a more uniform distribution. Also, electrified drops can be driven to overcome air resistance by suitable electric fields.
In many types of micro-electrical-mechanical-systems (MEMS) fluids are caused to move by the application of electric potentials. Usually this behavior is induced by electric forces acting on dielectric polarization charges generated at free fluid surfaces or at the interfaces between two fluids.

In some situations the effects of both dielectrically induced charges as well as free electric charges in a fluid must be considered. For these cases the fluid has some nonzero conductivity that must be accounted for by tracking charge densities and adding additional body forces to the fluid. The range of possibilities when conduction is present includes bound and free charges, recombination, ionization, currents without net charge densities, etc. As described next, we shall limit the present development to a useful subset of the many possibilities.

In this note we describe a set of program developments that give FLOW-3DÒ the capability to model fluid and particulate flows involving both free and induced charge densities. In the current released version of FLOW-3D® (Ver. 7.7) both particles and fluid can contain a fixed charge density, but there is no provision for dielectric materials.

Here we describe the addition of dielectric properties for particles, fluids, and solids. In addition, linear polarization forces acting on particles and fluids by electrostatic fields are added to the momentum equations for fluid and particles.

Self-Consistent Electric Fields and Electric Forces On Charged Particles

SCOPE
A recent addition to the computational fluid dynamics program FLOW-3D® is a capability for modeling discrete mass particles moving through a continuum. This model implicitly couples
the particles and continuum so that they may exchange momentum in a conservative way.
This report addresses how that model has been extended to account for mass particles having an electric charge and moving in an electric field. The extension is self-consistent in the sense that
the particle charges contribute to the electric field. For this reason the field is time dependent and must be recomputed for each time step of a numerical simulation.
In addition to the charged particles, solid objects (obstacles) located within the computational region may be assigned arbitrary, but constant in time, potentials. Each obstacle may have a
fixed potential value consistent with the obstacle being a conductor. A zero potential value is the default value if not otherwise specified. It should be noted that an electric potential can be
computed even when there are no charged particles, although this field will have no effect on flow processes unless the user adds some kind of additional interaction to the model.
Mesh boundaries that are rigid walls may be assigned non-zero potential values. All other boundaries are treated as symmetry boundaries with respect to the potential. Furthermore, no
insulated obstacles are allowed in this model. It is also assumed that if there are free fluid surfaces or fluid-fluid interfaces then the dielectric constants (i.e., ratios of material permittivities
to that of vacuum) of the different materials must be the same, otherwise additional development will be needed to solve for the electric potential. In general, this is not correct because the
dielectric constant does vary with material type; for example, water has a dielectric constant about 81 times that for air.