@article{ author = {Barner, B. J. and Corn, R. M.}, title = {ELECTROCHEMICAL AND VIBRATIONAL SPECTROSCOPIC STUDIES OF COADSORPTION - FORMATION OF MIXED MONOLAYERS OF METHYLENE-BLUE AND LONG-CHAIN DITHIOETHERS AT SULFUR-MODIFIED POLYCRYSTALLINE GOLD SURFACES}, journal = {Langmuir}, volume = {6}, number = {5}, pages = {1023-1030}, year = {1990} } @article{ author = {Barner, B. J. and Green, M. J. and Saez, E. I. and Corn, R. M.}, title = {POLARIZATION MODULATION FOURIER-TRANSFORM INFRARED REFLECTANCE MEASUREMENTS OF THIN-FILMS AND MONOLAYERS AT METAL-SURFACES UTILIZING REAL-TIME SAMPLING ELECTRONICS}, journal = {Analytical Chemistry}, volume = {63}, number = {1}, pages = {55-60}, abstract = {The technique of polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy is applied to the reflectance spectra of thin polymer films and spontaneously organized monolayers adsorbed onto gold, silver, and chromium surfaces. The differential PM-FTIR reflectance spectra are obtained by the photoelastic modulation of the FTIR beam polarization and a novel real-time sampling methodology that generated the average and differential FTIR interferograms from measurements of the infrared signal during each modulation cycle. In comparison with conventional electronics that utilize a lock-in amplifier, the real-time electronics permit the operation of the FTIR spectrometer at normal mirror velocities. The use of polarization-independent optics after the metal surface ensures that the true surface infrared differential reflectance spectrum is obtained. The theoretical wavelength dependence of the PM-FTIR spectrum is rederived for the case of the real-time sampling measurement and compared to the experimental data. Spectra of a 15-nm film of polylimide on chromium, a spontaneously organized monolayer of octadecanethiol on gold, and a spontaneously organized monolayer of arachidic acid on silver are shown to demonstrate the applicability of the method to different metals, samples, and spectral regions.}, year = {1991} } @article{ author = {Bell, S. A. and McLean, M. E. and Oh, S. K. and Tichy, S. E. and Zhang, W. and Corn, R. M. and Crooks, R. M. and Simanek, E. E.}, title = {Synthesis and characterization of covalently linked single-stranded DNA oligonucleotide-dendron conjugates}, journal = {Bioconjugate Chemistry}, volume = {14}, number = {2}, pages = {488-493}, year = {2003} } @article{ author = {Brockman, J. M. and Frutos, A. G. and Corn, R. M.}, title = {A multistep chemical modification procedure to create DNA arrays on gold surfaces for the study of protein-DNA interactions with surface plasmon resonance imaging}, journal = {Journal of the American Chemical Society}, volume = {121}, number = {35}, pages = {8044-8051}, abstract = {A multistep surface modification procedure for the creation of DNA arrays on chemically modified gold surfaces that can be used in surface plasmon resonance (SPR) imaging studies of protein-DNA interactions is demonstrated. The multistep procedure is required to create an array of spots that are surrounded first by a hydrophobic background which allows for the pinning of aqueous DNA solutions onto individual array elements and then to replace that hydrophobic background with one that resists the nonspecific adsorption of proteins during in situ SPR imaging measurements. An amine-terminated alkanethiol monolayer is employed as the base layer, and Fmoc and PEG modifiers are used to create the sequentially hydrophobic and protein adsorption-resistant surfaces, respectively. Specifically, the chemical modification steps are the following: (1) the adsorption and self-assembly of an 11-mercaptoundecylamine (MUAM) monolayer on an evaporated gold thin film, (2) the reaction of the MUAM monolayer with an Fmoc protecting group to create a hydrophobic surface, (3) the photopatterned removal of the alkanethiol followed by (4) the readsorption of MUAM to create an array of MUAM squares (750 x 750 mu m) surrounded bpa hydrophobic MUAM-Fmoc background that can pin drops of aqueous solution, (5) the attachment of oligonucleotide sequences onto the MUAM squares by the reaction of the amine-terminated surface with the heterobifunctional cross linker SSMCC followed by a coupling reaction to a small volume (0.1 mu L) of thiol-modified DNA, and (6) the removal of the Fmoc protecting group followed by (7) a pegylation reaction of the MUAM with PEG-NHS to create a protein adsorption-resistant background. A combination of polarization-modulation FTIR spectroscopy, contact angle, and scanning angle SPR measurements is used to characterize the surface modification procedure. An SPR imaging measurement of the adsorption of single-stranded DNA binding protein (SSB) onto an oligonucleotide array created by this procedure is used to demonstrate the utility of these surfaces.}, year = {1999} } @article{ author = {Brockman, J. M. and Nelson, B. P. and Corn, R. M.}, title = {Surface plasmon resonance imaging measurements of ultrathin organic films}, journal = {Annual Review of Physical Chemistry}, volume = {51}, pages = {41-63}, year = {2000} } @article{ author = {Campbell, D. J. and Barner, B. J. and Lynch, M. L. and Corn, R. M.}, title = {STUDIES OF MOLECULAR-ORIENTATION IN MIXED MONOLAYERS AT METAL-ELECTRODES BY OPTICAL 2ND HARMONIC-GENERATION AND VIBRATIONAL SPECTROSCOPY}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {198}, pages = {56-COLL}, year = {1989} } @article{ author = {Campbell, D. J. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF HYDROGEN EVOLUTION FROM POLYCRYSTALLINE SILVER ELECTRODES IN ACETONITRILE}, journal = {Journal of Physical Chemistry}, volume = {91}, number = {22}, pages = {5668-5673}, year = {1987} } @article{ author = {Campbell, D. J. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF CHEMISORPTION AT ELECTRODE SURFACES}, journal = {Acs Symposium Series}, volume = {378}, pages = {294-302}, year = {1988} } @article{ author = {Campbell, D. J. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF POLYCRYSTALLINE PLATINUM-ELECTRODES IN SULFURIC AND PERCHLORIC-ACID SOLUTIONS}, journal = {Journal of Physical Chemistry}, volume = {92}, number = {20}, pages = {5796-5800}, year = {1988} } @article{ author = {Campbell, D. J. and Higgins, D. A. and Corn, R. M.}, title = {MOLECULAR 2ND HARMONIC-GENERATION STUDIES OF METHYLENE-BLUE CHEMISORBED ONTO A SULFUR-MODIFIED POLYCRYSTALLINE PLATINUM-ELECTRODE}, journal = {Journal of Physical Chemistry}, volume = {94}, number = {9}, pages = {3681-3689}, year = {1990} } @article{ author = {Campbell, D. J. and Lynch, M. L. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF ANIONIC CHEMISORPTION AT POLYCRYSTALLINE PLATINUM-ELECTRODES}, journal = {Langmuir}, volume = {6}, number = {11}, pages = {1656-1664}, year = {1990} } @article{ author = {Cheng, Y. F. and Corn, R. M.}, title = {Ultrathin polypeptide multilayer films for the fabrication of model liquid/liquid electrochemical interfaces}, journal = {Journal of Physical Chemistry B}, volume = {103}, number = {41}, pages = {8726-8731}, abstract = {Ultrathin (<20 nm) polypeptide multilayer films are assembled by the electrostatic adsorption of alternating monolayers of poly(L-lysine) and poly(L-glutamic acid) onto carboxylic acid terminated alkanethiol-modified gold surfaces. These polypeptide multilayer films are hydrophilic, can bind electroactive anions such as ferri/ferrocyanide, and are stable when immersed in organic solvents such as 1,2-dichloroethane (1,2-DCE). A combination of ex situ polarization-modulation Fourier transform infrared reflection-absorption spectroscopy (PM-FTIRRAS) and surface plasmon resonance (SPR) measurements is used to characterize the film deposition and the incorporation of D2O and electroactive ions. Electrochemical cycling of the polypeptide films in 1,2-DCE is used to reversibly oxidize the ferrocyanide ions in the film, and in situ PM-FTIRRAS measurements demonstrate that more than 95% of the ferrocyanide ions can be converted to ferricyanide without loss to the organic phase. These ultrathin films will be used to study both ion and electron transport across the film/1,2-DCE interface.}, year = {1999} } @article{ author = {Cheng, Y. F. and Murtomaki, L. and Corn, R. M.}, title = {Electrochemical characterization of the ultrathin polypeptide film/1,2-dichloroethane liquid vertical bar liquid interface}, journal = {Journal of Electroanalytical Chemistry}, volume = {483}, number = {1-2}, pages = {88-94}, note = {Euroconference on Modern Trends in Electrochemistry of Molecular Interfaces AUG 28-SEP 03, 1999 KYRKSLATT, FINLAND}, abstract = {A model liquid \ liquid interface formed by an ultrathin hydrophilic polypeptide film at a chemically modified gold surface in contact with a 1,2-dichloroethane (DCE) electrolyte solution is characterized with a combination of electrochemical and in situ polarization modulation FTIR (PM-FTIR) measurements. The hydrophilic films are prepared by the sequential layer by layer electrostatic adsorption of the polypeptides poly-L-lysine and poly-L-glutamic acid onto gold thin films that have been derivatized with an omega-carboxylic acid functionalized alkanethiol monolayer. The polypeptide film thickness can be varied from 5 to 30 nm, and ionic electroactive species such as ferri/ferrocyanide can be incorporated into the film. The oxidation-reduction reactions of this electrochemical system are characterized with cyclic voltammetry and potential step measurements, and require both an electron transfer step at the gold \ film interface and an ion transfer step at the film \ DCE interface. No diffusion processes are observed in these ultrathin film systems, but the voltammetric response is asymmetric and broader than that observed in reversible monolayer systems. Based on digital simulations, the standard rate constant is estimated to be ca. 0.24 s(-1), and the standard deviation of the formal potential distribution is found to be approximately 130 mV. When the film is brought in contact with an organic solution containing decamethylferrocene, an electrocatalytic reaction is observed in the cyclic voltammetry corresponding to an electron transfer reaction across the film \ DCE interface. Tn situ PM-FTIR experiments show that the cyclic voltammetry samples only a fraction of the electroactive species in the polypeptide film. (C) 2000 Elsevier Science S.A. All rights reserved.}, year = {2000} } @article{ author = {Corn, R. M.}, title = {LIGHT-SCATTERING AND NONLINEAR OPTICS FROM THIN-FILM ELECTRODES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {190}, number = {SEP}, pages = {176-COL}, year = {1985} } @article{ author = {Corn, R. M.}, title = {2ND HARMONIC-GENERATION AT ELECTRODE SURFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {194}, pages = {108-COLL}, year = {1987} } @article{ author = {Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF CHEMISORPTION AT PLATINUM-ELECTRODES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {196}, pages = {146-COLL}, year = {1988} } @article{ author = {Corn, R. M.}, title = {RESONANT AND NONRESONANT 2ND-HARMONIC GENERATION STUDIES OF CHEMISORPTION AT PLATINUM-ELECTRODE SURFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {197}, pages = {74-COLL}, year = {1989} } @article{ author = {Corn, R. M.}, title = {ADSORPTION, ORIENTATION AND ORDER AT SURFACES AS STUDIED BY OPTICAL 2ND HARMONIC-GENERATION}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {202}, pages = {24-ANYL}, note = {1}, year = {1991} } @article{ author = {Corn, R. M.}, title = {OPTICAL 2ND HARMONIC-GENERATION STUDIES OF ADSORPTION, ORIENTATION, AND ORDER AT THE ELECTROCHEMICAL INTERFACE}, journal = {Analytical Chemistry}, volume = {63}, number = {5}, pages = {A285-&}, year = {1991} } @article{ author = {Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF PLATINUM SINGLE-CRYSTAL ELECTRODE SURFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {203}, pages = {308-COLL}, note = {1}, year = {1992} } @article{ author = {Corn, R. M.}, title = {FTIR AND OPTICAL 2ND-HARMONIC GENERATION STUDIES OF ORIENTATION AND ORDER IN MOLECULAR MONOLAYERS AT ELECTROCHEMICAL INTERFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {204}, pages = {38-COLL}, note = {1}, year = {1992} } @article{ author = {Corn, R. M.}, title = {MOLECULAR ADSORPTION AND ORIENTATION AT SURFACES AS STUDIED BY 2ND HARMONIC-GENERATION}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {203}, pages = {177-ANYL}, note = {1}, year = {1992} } @article{ author = {Corn, R. M.}, title = {OPTICAL 2ND HARMONIC-GENERATION STUDIES OF MOLECULAR-ORIENTATION AND ORDER AT LIQUID LIQUID SURFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {204}, pages = {104-PHYS}, note = {2}, year = {1992} } @article{ author = {Corn, R. M.}, title = {OPTICAL 2ND-HARMONIC GENERATION STUDIES OF LIQUID-LIQUID AND SEMICONDUCTOR ELECTROCHEMICAL INTERFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {207}, pages = {99-PHYS}, note = {2}, year = {1994} } @article{ author = {Corn, R. M.}, title = {Near IR surface plasmon resonance measurements of biopolymer adsorption: Scanning angle, imaging, and Fourier-transform methods}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {218}, pages = {U160-U160}, note = {1}, year = {1999} } @article{ author = {Corn, R. M.}, title = {Multistep surface modification procedure for the creation of DNA arrays on chemically modified gold surfaces}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {219}, pages = {U280-U280}, note = {2}, year = {2000} } @article{ author = {Corn, R. M.}, title = {Enzymatically amplified SPR imaging for biosensor microarrays: Fighting the tyranny of the Langmuir isotherm}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {230}, pages = {U330-U331}, note = {230th National Meeting of the American-Chemical-Society AUG 28-SEP 01, 2005 Washington, DC}, year = {2005} } @article{ author = {Corn, R. M. and Higgins, D. A.}, title = {OPTICAL 2ND-HARMONIC GENERATION ASS PROBE OF SURFACE-CHEMISTRY}, journal = {Chemical Reviews}, volume = {94}, number = {1}, pages = {107-125}, year = {1994} } @article{ author = {Corn, R. M. and Hurtt, G. and Smith, E. and Nelson, B. and Grimsrud, T.}, title = {Surface plasmon resonance imaging measurements of DNA, RNA, and protein adsorption onto DNA monolayer arrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {220}, pages = {U272-U272}, note = {1}, year = {2000} } @article{ author = {Corn, R. M. and Lee, H. J.}, title = {Surface enzyme reactions for enhanced biosensing of DNA and RNA microarrays with SPR imaging}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {230}, pages = {U321-U321}, note = {230th National Meeting of the American-Chemical-Society AUG 28-SEP 01, 2005 Washington, DC}, year = {2005} } @article{ author = {Corn, R. M. and Lee, H. J. and Goodrich, T. T.}, title = {Enzymatic methods for SPR imaging measurements of DNA and protein microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {227}, pages = {U114-U114}, note = {227th National Meeting of the American-Chemical Society MAR 28-APR 01, 2004 Anaheim, CA}, year = {2004} } @article{ author = {Corn, R. M. and Lee, H. J. and Wegner, G. J. and Goodrich, T. T. and Smith, E. A.}, title = {SPR imaging measurements of DNA, peptide and protein microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {225}, pages = {U622-U622}, note = {225th National Meeting of the American-Chemical-Society MAR 23-27, 2003 NEW ORLEANS, LA}, year = {2003} } @article{ author = {Corn, R. M. and Lee, H. J. and Wegner, G. J. and Smith, E. A. and Goodrich, T. T. and Codner, E.}, title = {SPR imaging measurements for the rapid microarray detection of nucleic acids and proteins}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {225}, pages = {U107-U107}, note = {225th National Meeting of the American-Chemical-Society MAR 23-27, 2003 NEW ORLEANS, LA}, year = {2003} } @article{ author = {Corn, R. M. and Naujok, R. N. and Paul, H. J.}, title = {OPTICAL SHG MEASUREMENTS OF ADSORPTION AT THE LIQUID-LIQUID ELECTROCHEMICAL INTERFACE}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {210}, pages = {1-COLL}, note = {1}, year = {1995} } @article{ author = {Corn, R. M. and Nelson, B. P. and Smith, E. and Hurtt, G.}, title = {Surface plasmon resonance imaging studies of DNA and protein microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {221}, pages = {U359-U359}, note = {2}, year = {2001} } @article{ author = {Corn, R. M. and Paul, H. J.}, title = {Second harmonic generation measurements of electrostatic biopolymer-surfactant coadsorption at the liquid/liquid interface}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {214}, pages = {136-PHYS}, note = {2}, year = {1997} } @article{ author = {Corn, R. M. and Philpott, M. R.}, title = {SURFACE PLASMON-ENHANCED RAMAN-SCATTERING AT THIN SILVER FILMS}, journal = {Journal of Chemical Physics}, volume = {80}, number = {10}, pages = {5245-5249}, year = {1984} } @article{ author = {Corn, R. M. and Philpott, M. R.}, title = {THE INTERPRETATION OF VERY LOW-FREQUENCY RAMAN-SCATTERING FROM ROUGHENED SILVER ELECTRODES - CLUSTERS, CAVITIES, OR COMPLEXES}, journal = {Journal of Chemical Physics}, volume = {81}, number = {9}, pages = {4138-4142}, year = {1984} } @article{ author = {Corn, R. M. and Romagnoli, M. and Levenson, M. D. and Philpott, M. R.}, title = {2ND HARMONIC-GENERATION AT THIN-FILM SILVER ELECTRODES VIA SURFACE-POLARITONS}, journal = {Journal of Chemical Physics}, volume = {81}, number = {9}, pages = {4127-4132}, year = {1984} } @article{ author = {Corn, R. M. and Romagnoli, M. and Levenson, M. D. and Philpott, M. R.}, title = {2ND-HARMONIC GENERATION FROM THIN-FILM SILVER ELECTRODES VIA SURFACE-PLASMONS}, journal = {Journal of the Optical Society of America B-Optical Physics}, volume = {1}, number = {3}, pages = {446-446}, year = {1984} } @article{ author = {Corn, R. M. and Romagnoli, M. and Levenson, M. D. and Philpott, M. R.}, title = {THE POTENTIAL DEPENDENCE OF SURFACE PLASMON-ENHANCED 2ND-HARMONIC GENERATION AT THIN-FILM SILVER ELECTRODES}, journal = {Chemical Physics Letters}, volume = {106}, number = {1-2}, pages = {30-35}, year = {1984} } @article{ author = {Corn, R. M. and Shannon, V. L. and Snyder, R. G. and Strauss, H. L.}, title = {ORIENTATIONAL DYNAMICS AND DISORDER OF SOLID ADAMANTANE AS STUDIED BY INFRARED-SPECTROSCOPY}, journal = {Journal of Chemical Physics}, volume = {81}, number = {12}, pages = {5231-5238}, year = {1984} } @article{ author = {Corn, R. M. and Smith, E. A. and Wegner, G. J. and Goodrich, T. T. and Lee, H. J.}, title = {SPR imaging measurements of DNA, peptide and protein microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {224}, pages = {U151-U151}, note = {1}, year = {2002} } @article{ author = {Corn, R. M. and Strauss, H. L.}, title = {AN INFRARED STUDY OF THE DYNAMICS OF WEAKLY BOUND WATER IN CRYSTALLINE HYDRATES}, journal = {Journal of Chemical Physics}, volume = {76}, number = {10}, pages = {4834-4843}, year = {1982} } @article{ author = {Corn, R. M. and Strauss, H. L.}, title = {AMMONIUM ION ROTATION IN AMMONIUM-PERCHLORATE AS STUDIED BY INFRARED-SPECTROSCOPY}, journal = {Journal of Chemical Physics}, volume = {79}, number = {6}, pages = {2641-2649}, year = {1983} } @article{ author = {Duevel, R. V. and Corn, R. M.}, title = {AMIDE AND ESTER SURFACE ATTACHMENT REACTIONS FOR ALKANETHIOL MONOLAYERS AT GOLD SURFACES AS STUDIED BY POLARIZATION MODULATION FOURIER-TRANSFORM INFRARED-SPECTROSCOPY}, journal = {Analytical Chemistry}, volume = {64}, number = {4}, pages = {337-342}, abstract = {The modification of alkanethiol monolayers via amide and ester formation reactions is demonstrated as a methodology for attaching monolayer and submonolayer coverages of specific chemical species onto metal electrodes. A monolayer of 11-mercaptoundecanoic acid (HSC10H20COOH) is used as a surface bifunctional linking agent on polycrystalline gold surfaces. The reaction of these adsorbed molecules with gaseous thionyl chloride converts the carboxylic acid group to an acid chloride which can then be reacted further with an amine or alcohol to form an amide or ester linkage. The attachment of alkyl, aromatic, and electrochemically active species to the surface is reported to demonstrate the versatility of this surface derivatization chemistry. Polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy is employed as the primary method for monitoring the chemical structure of the adsorbed monolayers, and additional X-ray photoelectron spectroscopy (XPS) and electrochemical measurements are used to verify the elemental composition, oxidation state, and surface coverage of the adsorbed molecules.}, year = {1992} } @article{ author = {Duevel, R. V. and Corn, R. M. and Liu, M. D. and Leidner, C. R.}, title = {ORIENTATION AND ORGANIZATION IN FUNCTIONALIZED PHOSPHOLIPID MONOLAYERS AT GOLD SURFACES AS MEASURED BY POLARIZATION MODULATION FOURIER-TRANSFORM INFRARED-SPECTROSCOPY}, journal = {Journal of Physical Chemistry}, volume = {96}, number = {1}, pages = {468-473}, abstract = {Polarization modulation Fourier transform infrared reflectance (PM-FTIR) spectroscopy has been employed to study the pressure-dependent molecular structure of functionalized phospholipid monolayers at the gold-air interface. "Head-down" monolayers of dipalmitoylphosphatidylcholine (DPPC) and the anthraquinone- and anthracene-functionalized analogues (DPPC-AQ and DPPC-AN) have been prepared on vapor-deposited polycrystalline gold surfaces using Langmuir-Blodgett techniques. PM-FTIR spectra of monolayers deposited with varying molecular densities reveal differing degrees of order within the aliphatic chains and slight changes in orientation of the aromatic rings. The molecular order within the alkyl chains can be estimated from relative peak frequencies and intensities in the CH stretching region and follows the trend DPPC > DPPC-AQ > DPPC-AN. More expanded films of all three amphiphiles are found to possess more disordered alkyl chains. The relative intensities of the carbonyl and ring stretch bands of DPPC-AQ have been employed to estimate the molecular orientation of the anthraquinone moieties within the monolayer. The PM-FTIR spectroscopic results are used to refine the conclusions of previous film balance, electrochemical, and ellipsometric studies of the functionalized phospholipids within the free and supported monolayers.}, year = {1992} } @article{ author = {Facci, J. S. and Liu, M. D. and Leidner, C. R. and Corn, R. M.}, title = {MOLECULAR-LEVEL VIEW OF REDOX ASSEMBLIES OF PHOSPHOLIPID QUINONE MONOLAYERS AT AIR-WATER AND GOLD-WATER INTERFACES}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {204}, pages = {123-COLL}, note = {1}, year = {1992} } @article{ author = {Fang, S. and Lee, H. J. and Wark, A. W. and Kim, H. M. and Corn, R. M.}, title = {Determination of ribonuclease H surface enzyme kinetics by surface plasmon resonance imaging and surface plasmon fluorescence spectroscopy}, journal = {Analytical Chemistry}, volume = {77}, number = {20}, pages = {6528-6534}, year = {2005} } @article{ author = {Fang, S. P. and Lee, H. J. and Wark, A. W. and Corn, R. M.}, title = {Attomole microarray detection of MicroRNAs by nanoparticle-amplified SPR imaging measurements of surface polyadenylation reactions}, journal = {Journal of the American Chemical Society}, volume = {128}, number = {43}, pages = {14044-14046}, year = {2006} } @article{ author = {Frey, B. L. and Corn, R. M.}, title = {Covalent attachment and derivatization of poly(L-lysine) monolayers on gold surfaces as characterized by polarization-modulation FT-IR spectroscopy}, journal = {Analytical Chemistry}, volume = {68}, number = {18}, pages = {3187-3193}, abstract = {A monolayer of poly(L-lysine) (PL) is attached covalently via amide bonds to an alkanethiol self-assembled monolayer (SAM) on a gold surface. The amide bond is formed in two steps: the terminal carboxylic acid groups of an 11-mercaptoundecanoic acid (MUA) SAM are first activated to the N-hydroxysulfosuccinimide (NHSS) ester, followed by reaction of this MUA-NHSS ester monolayer with the amino groups of PL to create multiple amide bond linkages to the surface. The reactivity and packing density of the MUA-NHSS esters are investigated in detail by reacting these intermediates with ammonia (NH3). In the NH3 experiments, approximately 50% of the carboxylic acids in the MUA monolayer are converted to amides during the first cycle of this two-step surface reaction. This reaction yield of 50% is limited by the steric packing of the NHSS ester intermediate. However, after three cycles of MUA activation to the NHSS ester and reaction with NH3, nearly all of the MUA molecules (similar to 80%) are converted to amides. Polarization-modulation Fourier transform infrared reflection-absorption spectroscopy (PM-FT-IRRAS) is employed to study both the NH3 and PL reactions on the gold surface. The PM-FT-IRRAS spectrum of a covalently attached PL monolayer indicates that amide bonds are formed with the underlying MUA molecules. This conclusion is confirmed by the fact that the covalent PL monolayer resists desorption despite immersion into solutions of pH < 2 or pH > 12, Finally, the PL is derivatized with a bifunctional NHSS ester-maleimide molecule either by reaction in solution prior to covalent attachment or by reaction with PL already adsorbed to the surface. Up to 50% of the total number of lysine amino groups are converted to maleimide groups, which can be used for the subsequent attachment of sulfhydryl-containing biomolecules.}, year = {1996} } @article{ author = {Frey, B. L. and Hanken, D. G. and Corn, R. M.}, title = {VIBRATIONAL SPECTROSCOPIC STUDIES OF THE ATTACHMENT CHEMISTRY FOR ZIRCONIUM PHOSPHONATE MULTILAYERS AT GOLD AND GERMANIUM SURFACES}, journal = {Langmuir}, volume = {9}, number = {7}, pages = {1815-1820}, abstract = {The attachment chemistry required for the sequential self-assembly of zirconium phosphonate (ZP) monolayers on gold and germanium surfaces is examined with a combination of attenuated total reflection (ATR-FTIR) and polarization modulation (PM-FTIR) Fourier transform infrared spectroscopies. On the germanium substrates, the conversion of an attached omega-aminosilane monolayer to phosphate amide species creates a primer for the sequential deposition of multilayer films of zirconium 1,10-decanediylbis-(phosphonate)(Zr/DBP). On vapor-deposited gold films, a packed monolayer of 11-mercapto-1-undecanol (MUD) serves as the basis for a primer monolayer. PM-FTIR measurements show that phosphorylation of the terminal hydroxy groups results in a surface with a mixture of phosphate mono- and diesters, which bind Zr4+ to commence the self-assembly of the Zr/DBP multilayers. On both substrates, the alkyl chain regions of the ZP film are observed to be conformationally disordered due to the control of the lateral spacing in the films by the inorganic (phosphonate-Zr-phosphonate) regions. Furthermore, the packing density, order, and chemical structure of the primer layer are found to influence the resulting ZP multilayer structure.}, year = {1993} } @article{ author = {Frey, B. L. and Jordan, C. E. and Kornguth, S. and Corn, R. M.}, title = {CONTROL OF THE SPECIFIC ADSORPTION OF PROTEINS ONTO COLD SURFACES WITH POLY(L-LYSINE) MONOLAYERS}, journal = {Analytical Chemistry}, volume = {67}, number = {24}, pages = {4452-4457}, abstract = {Monolayers of the polypeptide poly(L-lysine) (PL) are used to control the specific adsorption of proteins onto gold surfaces. A PL monolayer modified with biotin is electrostatically adsorbed onto a vapor-deposited gold film that has been coated with a self-assembled monolayer of the alkanethiol 11-mercaptoundecanoic acid (MUA). The immobilized biotin moieties act as specific adsorption sites for the protein avidin. Adsorption of the biopolymers onto the gold surface is monitored with a combination of surface plasmon resonance (SPR) and fluorescence measurements. By varying the percent biotinylation of the lysine residues on the PL prior to deposition, the surface coverage of avidin can be controlled to create either full or partial monolayers. The thickness of a full monolayer of avidin is 41 Angstrom, as determined by the SPR measurements. At high surface coverages of avidin, an excess of biotin sites is required to overcome steric hindrance. The PL monolayer and any adsorbed avidin can be easily rinsed from the surface with a low or high pH solution. This removal allows for quantitation of the adsorbed molecules by fluorescence measurements in solution rather than on the gold surface. In this manner, fluorescein-labeled PL and avidin are used to determine absolute surface coverages of 4 x 10(14) lysine residues cm(-2) for the PL monolayer and 3 x 10(12) avidin molecules cm(-2) for the full avidin monolayer. SPR imaging experiments are employed to verify that UV photopatterning of the MUA/PL bilayers can be used to spatially direct the adsorption of avidin onto the gold surface. The polylysine attachment methodology will be beneficial in the fabrication of adsorption biosensors.}, year = {1995} } @article{ author = {Frutos, A. G. and Brockman, J. M. and Corn, R. M.}, title = {Reversible protection and reactive patterning of amine- and hydroxyl-terminated self-assembled monolayers on gold surfaces for the fabrication of biopolymer arrays}, journal = {Langmuir}, volume = {16}, number = {5}, pages = {2192-2197}, abstract = {The reversible protection of amine- and hydroxyl-terminated alkanethiol self-assembled monolayers (SAMs) on gold surfaces using the base-labile protecting group 9-fluorenylmethoxycarbonyl (Fmoc) and the acid-labile protecting group dimethoxytrityl (DMT) is described. When used in combination with UV photopatterning or mu-contact printing techniques, his reversible SAM protection chemistry can be used to control the reactivity and wettability of different portions of the surface. Such spatial control is utilized in the fabrication of DNA arrays. Specifically, gold surfaces modified with the amine-terminated alkanethiol 11-mercaptoundecylamine (MUAM) are reacted with an N-hydroxysuccinimide (NHS) ester derivative of Fmoc, forming a covalent urethane (carbamate) linkage and converting the initially hydrophilic MUAM surface to a hydrophobic, Fmoc-terminated surface. Upon exposure of the Fmoc-modified surface to a solution of a secondary amine, the Fmoc is cleaved, regenerating the original hydrophilic MUAM surface. Fmoc is also utilized as a hydroxyl protecting group, as demonstrated by the reaction of Fmoc-Cl with a monolayer of 11-mercaptoundecanol (MUD). The hydrophobic protecting group DMT is reacted with the w-hydroxyl groups of both MUD and poly(ethylene glycol)-terminated alkanethiol (PEG-SH) SAMs to form an acid labile ether bond; removal of the DMT group is accomplished by soaking the surface in 3% trifluoracetic acid. A combination of polarization-modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS), surface plasmon resonance (SPR), and contact angle measurements is used to characterize the attachment and subsequent removal of the protecting groups. To demonstrate one application of this SAM protection chemistry and reactive patterning, a DNA array is fabricated and used in an SPR imaging measurement of the adsorption of the mismatch binding protein MutS.}, year = {2000} } @article{ author = {Frutos, A. G. and Corn, R. M.}, title = {SPR of ultrathin organic films}, journal = {Analytical Chemistry}, volume = {70}, number = {13}, pages = {449A-455A}, year = {1998} } @article{ author = {Frutos, A. G. and Liu, Q. H. and Thiel, A. J. and Sanner, A. M. W. and Condon, A. E. and Smith, L. M. and Corn, R. M.}, title = {Demonstration of a word design strategy for DNA computing on surfaces}, journal = {Nucleic Acids Research}, volume = {25}, number = {23}, pages = {4748-4757}, abstract = {A strategy for DNA Computing on surfaces using linked sets of 'DNA words' that are short oligonucleotide's (16mers) is proposed. The 16mer words have the format 5'-FFFFvvvvvvvvFFFF-3' in which 4-8 bits of data are stored in 8 variable ('v') base locations, and the remaining fixed ('F') base locations are used as a word label. Using a template and map strategy, a set of 108 8mers each of which possesses at least a 4 base mismatch with the complements to all the other members of the set (4bm complements) are identified for use as a variable base sequence set, In addition, sets of 4 and 12 word labels of the form ABCD....DCBA that are respectively 8bm and 6bm complements with each other are identified. The 16mers are chosen to have a G/C content of 50% in order to make the thermodynamic stability of the perfectly matched hybridized DNA duplexes similar; a simple pairwise additive method is used to estimate the perfect match and mismatch hybridization thermodynamics. A series of preliminary experiments are presented that use small arrays of 18mers attached to chemically modified gold surfaces and fluorescently labeled complements to study the hybridization adsorption and enzymatic manipulation of the oligonucleotides.}, year = {1997} } @article{ author = {Frutos, A. G. and Smith, L. M. and Corn, R. M.}, title = {Enzymatic ligation reactions of DNA "words" on surfaces for DNA computing}, journal = {Journal of the American Chemical Society}, volume = {120}, number = {40}, pages = {10277-10282}, abstract = {The enzymatic manipulation of sets of short, 16-base oligonucleotides, or DNA "words", is demonstrated with applications toward DNA computing on surfaces. The enzyme T4 DNA ligase is used to ligate (join) DNA words on a chemically modified gold thin film. The efficiency of this surface ligation reaction is 80%, as determined by removal of the ligated molecules from the surface followed by gel electrophoresis, This surface ligation reaction is used in two new operations for DNA computing on surfaces. In a "Surface Word Append" operation, the complexity and information density of DNA word strands attached to gold surfaces are increased by appending additional words onto these word strands. The ligation reaction is also utilized as part of a "Two-Word Mark and Destroy" operation in which singly marked two-word DNA strands are selectively removed from the surface in the presence of doubly marked two-word strands. These new operations are essential for manipulation of the large combinatorial sets of linked DNA word strands required for DNA computing.}, year = {1998} } @article{ author = {Frutos, A. G. and Thiel, A. J. and Condon, A. E. and Smith, L. M. and Corn, R. M.}, title = {DNA computing at gold surfaces modified by self-assembled monolayers}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {214}, pages = {64-MTLS}, note = {2}, year = {1997} } @article{ author = {Frutos, A. G. and Weibel, S. C. and Corn, R. M.}, title = {Rear-infrared surface plasmon resonance measurements of ultrathin films. 2. Fourier transform SPR spectroscopy}, journal = {Analytical Chemistry}, volume = {71}, number = {18}, pages = {3935-3940}, abstract = {The application of surface plasmon resonance (SPR) measurements to the study of ultrathin organic films adsorbed onto gold surfaces utilizing near-infrared (NIR) excitation from a Fourier transform (FT) spectrometer is described. The FT-SPR experiment measures the NIR reflectivity spectrum from a prism/gold film/water assembly at a fixed angle of incidence approximately 1-2 degrees greater than the critical angle. A strong reflectivity minimum is observed in the FT-SPR spectrum; this minimum can be shifted from 12 000 to 6000 cm(-1) by tuning the angle of incidence. Upon adsorption of a thin biopolymer film from solution, a shift in the minimum is observed that can be correlated to a film thickness using Fresnel calculations. From experiments on the adsorption of electrostatically bound poly(lysine)/poly(glutamic acid) multilayers, an similar to 60-cm(-1) shift per 10-Angstrom change in film thickness was measured. Frequency shifts of 2 cm(-1) (corresponding to a thickness change of the polymer layer of similar to 0.3 Angstrom) can be easily measured from the FT-SPR spectra, demonstrating that this technique has sensitivity equivalent to or better than other visible SPR angle shift or wavelength shift measurements. Furthermore, the ability to perform FT-SPR measurements over a wide range of NIR wavelengths allows one to avoid any absorption bands that might otherwise interfere with the analysis.}, year = {1999} } @article{ author = {Goodrich, T. T. and Lee, H. J. and Corn, R. M.}, title = {Direct detection of genomic DNA by enzymatically amplified SPR imaging measurements of RNA microarrays}, journal = {Journal of the American Chemical Society}, volume = {126}, number = {13}, pages = {4086-4087}, year = {2004} } @article{ author = {Goodrich, T. T. and Lee, H. J. and Corn, R. M.}, title = {Enzymatically amplified surface plasmon resonance imaging method using RNase H and RNA microarrays for the ultrasensitive detection of nucleic acids}, journal = {Analytical Chemistry}, volume = {76}, number = {21}, pages = {6173-6178}, year = {2004} } @article{ author = {Green, M. J. and Barner, B. J. and Corn, R. M.}, title = {REAL-TIME SAMPLING ELECTRONICS FOR DOUBLE MODULATION EXPERIMENTS WITH FOURIER-TRANSFORM INFRARED SPECTROMETERS}, journal = {Review of Scientific Instruments}, volume = {62}, number = {6}, pages = {1426-1430}, abstract = {A novel synchronous real-time analog sampling method for obtaining the sum and difference interferograms in double modulation Fourier transform infrared absorption experiments is described, and the application of this sampling methodology to polarization-modulation FTIR measurements of thin films at metal surfaces is demonstrated. A quadratic approximation of the background signal is used to calculate the difference interferogram. The demodulation of a test waveform with the real-time sampling electronics reveals how the bandwidth limitations of previous double modulation experiments on FTIR interferometers that employed lock-in amplifiers have been eliminated.}, year = {1991} } @article{ author = {Hanken, D. G. and Corn, R. M.}, title = {Electric field measurements inside self-assembled multilayer films at electrode surfaces by electrochemically modulated surface plasmon resonance experiments}, journal = {Israel Journal of Chemistry}, volume = {37}, number = {2-3}, pages = {165-172}, abstract = {The new in situ optical technique of electrochemically modulated surface plasmon resonance (EM-SPR) is described and applied to the measurement of the electrostatic fields inside noncentrosymmetric zirconium phosphonate (ZP) films formed from the asymmetric nonlinear optical material [1-[4-[4-[(N-(2-hydroxyethyl) -N-methyl)amino]phenyl]azo](5-phosphonopentyl)] pyridinium bromide (PY-AZO). In situ EM-SPR measurements on PY-AZO films yield a value for the change in electric field strength (Delta E) of 4 x 10(3) V/cm for a change in electrode potential (Delta phi(m)) at 0.0 V vs. SCE of +/-25 mV (8 x 10(4) V/cm for Delta phi(m) = 1 V). This electric field strength value indicates that there is substantial ion penetration into the film in the electrochemical environment. Both the phase and magnitude of the surface optical response in the EM-SPR measurements are used to distinguish the molecular and metal electrode contributions to the overall optical signal. These two EM-SPR contributions are identified and separated in a quantitative fashion through a series of theoretical Fresnel calculations.}, year = {1997} } @article{ author = {Hanken, D. G. and Corn, R. M.}, title = {Electric fields and interference effects inside noncentrosymmetric multilayer films at electrode surfaces from electrochemically modulated surface plasmon resonance experiments}, journal = {Analytical Chemistry}, volume = {69}, number = {18}, pages = {3665-3673}, abstract = {The electric field profile inside a self-assembled noncentrosymmetric zirconium phosphonate (ZP) multilayer film at a gold electrode is determined by the in situ optical technique of electrochemically modulated surface plasmon resonance (EM-SPR). In these experiments, changes in the index of refraction (Delta n) of a ZP film during potential modulation are measured via the EM-SPR differential reflectivity curves. Modulated SPR experiments on the ZP films incorporated into air-gap capacitors are used to relate Delta n to changes in the electric field strength (Delta E) inside the film. The noncentrosymmetric ZP films utilize the nonlinear optical chromophores [5-[4-[[4-[(6-hydroxyhexyl)sulfonyl]phenyl]azo]phenyl]pentoxy]phosphonic acid (HAPA) and [1-[4-[4-[(N-(2-hydroxyethyl)-N-methyl)amino]phenyl]azo](5-phosphonopent yl)]pyridium bromide (PY-AZO). For a 6.7 nn ZP HAPA film, a change in electrode potential (Delta phi(m)) of 50 mV corresponds to a change in electric field strength (Delta E) of 1.4 x 10(4) V/cm. EM-SPR experiments on mixed ZP multilayers of HAPA and the centrosymmetric molecule 1,10-decanediylbis(phosphonate) are used to measure the spatial variations of the electric fields within the ultrathin films. Evidence for ion and solvent penetration into the ZP films is observed in the electrochemical environment. Additional studies of interference effects in mixed multilayers of HAPA and PY-AZO are used to verify the retention of directional order during the ZP multilayer deposition process.}, year = {1997} } @article{ author = {Hanken, D. G. and Jordan, C. E. and Frey, B. L. and Corn, R. M.}, title = {Surface plasmon resonance measurements of ultrathin organic films at electrode surfaces}, journal = {Electroanalytical Chemistry, Vol 20}, volume = {20}, pages = {141-225}, year = {1998} } @article{ author = {Hanken, D. G. and Naujok, R. N. and Corn, R. M.}, title = {Surface plasmon resonance measurements of electrostatic fields in noncentrosymmetric azobenzene/zirconium phosphonate multilayers at electrochemical interfaces}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {212}, pages = {191-COLL}, note = {1}, year = {1996} } @article{ author = {Hanken, D. G. and Naujok, R. R. and Gray, J. M. and Corn, R. M.}, title = {Synthesis, spectroscopic characterization, and electro-optical properties of noncentrosymmetric azobenzene/zirconium phosphonate multilayer films}, journal = {Analytical Chemistry}, volume = {69}, number = {2}, pages = {240-248}, abstract = {Ultrathin noncentrosymmetric nonlinear optical films based on zirconium phosphonate (ZP) self-assembled multilayers that incorporate the asymmetric azobenzene chromophore [5-[4-[[4-[(6-hydroxyhexyl)sulfonyl]phenyl] azo]phenyl]pentoxy]phosphonic acid (HAPA) are synthesized and constructed, The ZP film structure and multilayer deposition chemistry are characterized by a combination of polarization/modulation Fourier transform infrared reflection absorption spectroscopy, surface plasmon resonance (SPR) measurements, and optical second harmonic generation (SHG). SPR measurements on the HAPA multilayer films yield an average monolayer thickness of 27 +/- 0.5 Angstrom. The resonant SHG at 365 nm from ultrathin HAPA ZP films on silica surfaces increases quadratically with the number of self-assembled HAPA monolayers, and an analysis of the polarization dependence of the surface SHG yields an orientation parameter LI = 0.79 +/- 0.03 corresponding to an average tilt angle of 27 +/- 2 degrees for the azobenzene chromophores with respect to the surface normal. An electro-optic coefficient r(33) for the HAPA monolayers of 11 pm/V at 632.8 nm is obtained from SPR modulation experiments of ZP films on gold substrates that have been incorporated into air-gap capacitors, SPR modulation experiments are then performed on a HAPA monolayer in an in situ electrochemical environment in order to determine that a modulation of +/- 25 mV corresponds to a change in the electric field strength of 1 x 10(-1) V/cm within the ultrathin organic film at the electrode surface.}, year = {1997} } @article{ author = {Hanken, H. G. and Corn, R. M.}, title = {VARIABLE INDEX OF REFRACTION ULTRATHIN FILMS FORMED FROM SELF-ASSEMBLED ZIRCONIUM PHOSPHONATE MULTILAYERS - CHARACTERIZATION BY SURFACE-PLASMON RESONANCE MEASUREMENTS AND POLARIZATION/MODULATION FT-IR SPECTROSCOPY}, journal = {Analytical Chemistry}, volume = {67}, number = {20}, pages = {3767-3774}, abstract = {Ultrathin (submicrometer) organic films of specified index of refraction are constructed by the sequential deposition of self-assembled zirconium phosphonate (ZP) molecular monolayers that contain two different bisphosphonate ions, 1,10-decanediylbis(phosphonate) (BP) and 4,4'azobis[(p-phenylene)methylene]bis(phosphate) (AZO). By varying the ratio of DBP to AZO monolayers in the ZP multilayer film, the index of refraction can be controlled. A combination of surface plasmon resonance (SPR) measurements and polarization/modulation Fourier transform infrared reflection-absorption spectroscopy (PM/FT-IRRAS) is used to examine the structure of the ZP multilayers on vapor-deposited gold substrates, and ellipsometric measurements are utilized to determine the index of refraction of the ZP multilayers on transparent substrates. ZP films consisting of 100% DBP and 100% AZO molecules are found to have indices of refraction of 1.51 and 1.64, respectively, at an optical wavelength of 632.8 mn. In both the 100% DBP and the 100% AZO multilayers, an average monolayer thickness of 16 +/- 0.5 A is determined from the SPR measurements. The spectroscopic and ellipsometric data indicate that the index of refraction of mixed ZP multilayer films (i.e., films with both DBP and AZO self-assembled monolayers) can be varied systematically between 1.51 and 1.64, but that the average thickness of the self-assembled monolayers is greater in the mixed films than in either of the 100% DBP or 100% AZO multilayers.}, year = {1995} } @article{ author = {Higgins, D. A. and Abrams, M. B. and Byerly, S. K. and Corn, R. M.}, title = {RESONANT 2ND HARMONIC-GENERATION STUDIES OF P-NITROPHENOL ADSORPTION AT CONDENSED-PHASE INTERFACES}, journal = {Langmuir}, volume = {8}, number = {8}, pages = {1994-2000}, abstract = {A comprehensive analysis of adsorption strength, average molecular orientation, and absolute molecular direction for p-nitrophenol at solid-air, solid-liquid, and liquid-air interfaces is obtained from the near-resonant optical second harmonic generation (SHG) from the interface. Perturbation theory calculations of the molecular nonlinear polarizability tensor elements using pi-electron wave functions are used to identify the dominant tensor elements. The near-resonant SHG from a monolayer of p-nitrophenol is shown to require the use of two molecular nonlinear polarizability tensor elements in the equations relating the experimentally measured SHG to the average molecular orientation in the monolayer and therefore cannot be correctly described with the usual assumption of the complete dominance of a single molecular nonlinear polarizability tensor element. The average molecular orientation within the adsorbed monolayer is then obtained from the polarization dependence of the surface SHG and is described by the orientation parameter, D = [cos3-theta]/[cos-theta], where theta is the angle between the molecular symmetry axis and the surface normal. A more realistic description of the molecular orientation is obtained by allowing for a partial Gaussian distribution in the angle-theta. Additional measurements of the phase of the surface SHG are used in conjunction with the theoretical calculations of the molecular nonlinear polarizability to ascertain the direction of the transition dipole moment relative to the surface.}, year = {1992} } @article{ author = {Higgins, D. A. and Byerly, S. K. and Abrams, M. B. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF METHYLENE-BLUE ORIENTATION AT SILICA SURFACES}, journal = {Journal of Physical Chemistry}, volume = {95}, number = {18}, pages = {6984-6990}, abstract = {The average molecular orientation of methylene blue molecules adsorbed onto a silica substrate is obtained from measurements of the resonant molecular optical second harmonic generation (SHG) from the interface at several wavelengths. A pi-electron nonlinear polarizability calculation is used to identify the primary molecular tensor elements responsible for the large nonlinear optical response of the adsorbed methylene blue. The polarization dependence of the SHG signal at three wavelengths is then used to calculate the average dye molecule orientation. Inclusion of the Fresnel coefficients of the interface and the dielectric constant for the methylene blue monolayer at both the fundamental and second harmonic wavelengths is required for the orientation calculation. Phase measurements of the surface nonlinear susceptibility are performed in order to demonstrate the complex nature of the SHG from the interface. The average methylene blue orientation is then determined by using both the polarization dependence and phase measurements of the nonlinear response. The SHG measurements presented here yield an average angle of 58-degrees between the long axis of the methylene blue molecule and the surface normal. Possible methylene blue dimer geometries on the surface are discussed in light of the SHG measurements.}, year = {1991} } @article{ author = {Higgins, D. A. and Corn, R. M.}, title = {2ND HARMONIC-GENERATION STUDIES OF ADSORPTION AT A LIQUID LIQUID ELECTROCHEMICAL INTERFACE}, journal = {Journal of Physical Chemistry}, volume = {97}, number = {2}, pages = {489-493}, abstract = {The technique of optical second harmonic generation (SHG) is applied to the measurement of molecular adsorption at the interface between two immiscible electrolyte solutions (ITIES). The resonant second harmonic response from 2-(n-octadecylamino)naphthalene-6-sulfonate (ONS) is used in conjunction with interfacial tension measurements to optically determine the relative surface coverage of the anionic surfactant molecule at a charged water-dichloroethane interface. At a pH of 9, ONS adsorption occurs at all potentials positive of the potential of zero charge. The potential-dependent adsorption of ONS can be described by a Frumkin isotherm with a free energy of adsorption that varies linearly with applied potential. The potential dependence of the SHG from the interface provides important information on the position of the adsorbed ONS molecules with respect to the ITIES. At a pH of 3, both the anionic form of ONS and the protonated zwitterionic form of ONS are present at the liquid-liquid interface. At very positive potentials, the anionic ONS at the interface undergoes a field-dependent conversion to the zwitterionic form.}, year = {1993} } @article{ author = {Higgins, D. A. and Naujok, R. R. and Corn, R. M.}, title = {2ND-HARMONIC GENERATION MEASUREMENTS OF MOLECULAR-ORIENTATION AND COADSORPTION AT THE INTERFACE BETWEEN 2 IMMISCIBLE ELECTROLYTE-SOLUTIONS}, journal = {Chemical Physics Letters}, volume = {213}, number = {5-6}, pages = {485-490}, abstract = {Resonant optical second harmonic generation (SHG) is obtained from monolayers of 4-n-octyloxybenzoic acid (OBA) and n-octyl-4-hydroxybenzoate (OHB) adsorbed at the water/1,2-dichloroethane interface. The polarization dependence of the SHG from pure monolayers of OBA and OHB indicates that the molecular axis of the OBA molecules is tilted 6-degrees closer to the surface normal than that of the OHB molecules. The SHG from a series of mixed monolayers of OBA and OHB exhibits interference effects that demonstrate that the dipole moments of the coadsorbed molecules are oriented in opposite directions at the interface.}, year = {1993} } @article{ author = {Jordan, C. E. and Corn, R. M.}, title = {Surface plasmon resonance imaging measurements of electrostatic biopolymer adsorption onto chemically modified gold surfaces}, journal = {Analytical Chemistry}, volume = {69}, number = {7}, pages = {1449-1456}, abstract = {A combination of in situ and ex situ surface plasmon resonance (SPR) imaging experiments is used to characterize the differential electrostatic adsorption of proteins and synthetic polypeptides onto photopatterned monolayers at gold surfaces. The nonspecific electrostatic adsorption of proteins onto negatively charged self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid (MUA) is found to depend on the protein pI, solution ionic strength, and solution pH. The pH dependence of the electrostatic adsorption of the protein avidin onto a MUA SAM indicates that a full monolayer adsorbs at a solution pH greater than 5.0, and an ''effective pK(a)'' of 3.6 is determined for the avidin adsorption, This effective pK(a) is a combination of the pK(a) of the MUA monolayer and the ion pairing adsorption coefficient for the avidin. Additional SPR imaging experiments show that the electrostatic adsorption of the synthetic polypeptide poly-L-lysine (PL) onto a MUA SAM varies with molecular weight, forming a full PL monolayer for polypeptides with more than 67 lysine residues.}, year = {1997} } @article{ author = {Jordan, C. E. and Frey, B. L. and Kornguth, S. and Corn, R. M.}, title = {CHARACTERIZATION OF POLY-L-LYSINE ADSORPTION ONTO ALKANETHIOL-MODIFIED GOLD SURFACES WITH POLARIZATION-MODULATION FOURIER-TRANSFORM INFRARED-SPECTROSCOPY AND SURFACE-PLASMON RESONANCE MEASUREMENTS}, journal = {Langmuir}, volume = {10}, number = {10}, pages = {3642-3648}, abstract = {The electrostatic adsorption of poly-L-lysine molecules onto a vapor-deposited gold film modified with a carboxylic acid-terminated alkanethiol monolayer is monitored with the spectroscopic techniques of polarization-modulation Fourier transform infrared (PM-FTIR) spectroscopy and surface plasmon resonance (SPR). The PIM-FTIR spectrum of a monolayer of poly-L-lysine (PL) adsorbed onto a self-assembled monolayer of 11-mercaptoundecanoic acid (MUA) indicates that the lysine residues and the MUA carboxylic acid moieties form ammonium - carboxylate ion pairs which electrostatically bind the polypeptide to the surface. The PL molecules can be desorbed from the surface by rinsing with a buffer solution at a pH that destroys the ion pairing (pH < 6.5 or pH > 12). Measurements of the shift in the SPR angle upon adsorption were used to determine the thicknesses of the adsorbed monolayers; the MUA and PL monolayers were found to be 17.0 and 10.5 Angstrom thick, respectively. These thickness results suggest that the poly-L-lysine monolayer adsorbs onto the packed MUA surface in an extended conformation with the PL backbone lying parallel to the surface. Subsequent exposure of the PL monolayer to a solution of iron phthalocyanine tetracarboxylic acid (FePc) resulted in the adsorption of a third layer onto the surface. The ability of the adsorbed PL molecules to interact with FePc indicates the presence of free lysine residues available for interaction with molecules other than the MUA monolayer.}, year = {1994} } @article{ author = {Jordan, C. E. and Frutos, A. G. and Thiel, A. J. and Corn, R. M.}, title = {Surface plasmon resonance imaging measurements of DNA hybridization adsorption and streptavidin/DNA multilayer formation at chemically modified gold surfaces}, journal = {Analytical Chemistry}, volume = {69}, number = {24}, pages = {4939-4947}, abstract = {A combination of scanning and imaging surface plasmon resonance (SPR) experiments is used to characterize DNA hybridization adsorption at gold surfaces and the subsequent immobilization of streptavidin. Single-stranded oligonucleotides are immobilized at gold surfaces, and the hybridization of biotinylated complements from solution is monitored with SPR. The subsequent attachment of streptavidin to the biotinylated complements provides a method of enhancing the SPR imaging signal produced as a result of the hybridization and leads to a 4-fold improvement in the hybridization detection limit of the SPR imaging apparatus. In situ scanning SPR experiments are used to measure a 60 +/- 20% hybridization efficiency between immobilized single-stranded DNA and biotinylated complements. From the information provided by both the in situ imaging and scanning SPR experiments, an absolute surface coverage of immobilized single-stranded DNA is estimated to be similar to 3 x 10(12) molecules/cm(2). The SPR signal resulting from hybridization onto immobilized probes is further amplified by the formation of streptavidin/DNA multilayers which grow by a combination of DNA hybridization and biotin-streptavidin binding. DNA/DNA multilayers without streptavidin are used as an additional method of amplifying the SPR signal.}, year = {1997} } @article{ author = {Kott, K. L. and Higgins, D. A. and McMahon, R. J. and Corn, R. M.}, title = {OBSERVATION OF PHOTOINDUCED ELECTRON-TRANSFER AT A LIQUID-LIQUID INTERFACE BY OPTICAL 2ND-HARMONIC GENERATION}, journal = {Journal of the American Chemical Society}, volume = {115}, number = {12}, pages = {5342-5343}, year = {1993} } @article{ author = {Lantz, J. M. and Baba, R. and Corn, R. M.}, title = {OPTICAL 2ND-HARMONIC GENERATION AS A PROBE OF ELECTROSTATIC FIELDS AND FLAT-BAND POTENTIAL AT SINGLE-CRYSTAL TIO2 ELECTRODES}, journal = {Journal of Physical Chemistry}, volume = {97}, number = {29}, pages = {7392-7395}, abstract = {The surface-sensitive technique of optical second harmonic generation (SHG) is applied to the measurement of dc electrostatic fields and the flatband potential at the TiO2 semiconductor electrode-electrolyte interface. A large SHG response is observed from n-type single-crystal TiO2(001) electrodes at potentials for which a depletion layer exists at the surface. This response is attributed to the electric field-induced SHG from the polarized TiO2 lattice in the space charge layer at the semiconductor surface. The SHG from the interface varies linearly with the applied potential and reaches a minimum at the flatband potential of the electrode. The potential at which this minimum occurs shifts with pH at the expected rate of 60 mV/pH unit. A simple model of the electrostatic fields as a function of the band bending at the interface can be used to explain the observed dependence of the SHG on applied potential. These experiments suggest that SHG can be used as a local, time-resolved spectroscopic measurement of the electrostatic fields and surface charge density at single-crystal TiO2 electrodes.}, year = {1993} } @article{ author = {Lantz, J. M. and Corn, R. M.}, title = {ELECTROSTATIC-FIELD MEASUREMENTS AND BAND FLATTENING DURING ELECTRON-TRANSFER PROCESSES AT SINGLE-CRYSTAL TIO2 ELECTRODES BY ELECTRIC-FIELD-INDUCED OPTICAL 2ND-HARMONIC GENERATION}, journal = {Journal of Physical Chemistry}, volume = {98}, number = {18}, pages = {4899-4905}, abstract = {Optical second harmonic generation (SHG) is employed as a local, time-resolved measurement of the electrostatic fields at the surface of single-crystal TiO2 electrodes in contact with aqueous electrolyte solutions. The interfacial SHG at a fundamental wavelength of 584 nm is dominated by the electric field-induced second harmonic (EFISH) response from the first 20 nm of the space charge layer at the surface of the semiconductor. A substantial decrease in the amount of SHG from the electrode while under potentiostatic control is observed upon illumination of the surface with UV light (320 nm) whose energy is above the bandgap for TiO2 (3.0 eV or 410 nm). Comparisons of the drop in SHG upon UV illumination with photovoltage measurements for TiO2 electrodes at open circuit verify that this decrease is due to a reduction in the strength of the electrostatic fields (''band flattening'') within the space charge region upon UV illumination. The EFISH response from the surface decreases with increasing power of the UV illumination, corresponding to a band flattening of up to 70% for the highest power densities. Upon termination of the UV illumination, a slow (10-12 s) rise time is observed for the return of the surface SHG to its normal levels. The unexpected length of this rise time is attributed to the chemical discharge of surface charge trap sites on the semiconductor electrode surface and can be shortened considerably by the addition of a hole scavenger such as sodium sulfite to the electrolyte solution.}, year = {1994} } @article{ author = {Lantz, J. M. and Corn, R. M.}, title = {TIME-RESOLVED OPTICAL 2ND-HARMONIC GENERATION MEASUREMENTS OF PICOSECOND BAND FLATTENING PROCESSES AT SINGLE-CRYSTAL TIO2 ELECTRODES}, journal = {Journal of Physical Chemistry}, volume = {98}, number = {38}, pages = {9387-9390}, abstract = {Time-resolved optical second harmonic generation (SHG) is used to probe the variations in the surface electrostatic fields that occur under pulsed UV (supra-bandgap) illumination at a n-TiO2(001) electrode. The interfacial SHG is dominated-by the electric field-induced second harmonic response from the first 20 nm of the,semiconductor surface; this large SHG signal decreases sharply under UV illumination due to the creation of a steady-state photogenerated hole population at the interface. An additional transient drop in SHG intensity is observed when the pump and probe beams are overlapped temporally on the TiO2 surface. The time scale for this additional band flattening is determined by the finite time required for photogenerated holes to migrate to the interface under the influence of the surface electrostatic fields. An average transit time of 25 ps that is independent of applied potential or solution composition is observed; this corresponds to a hole drift velocity of 4.0 x 10(4) cm s(-1) at the TiO2 surface. The SHG intensity is found to return to its steady-state level in 3-4 ns due to-the removal of the excess holes at the surface by, electrochemical charge transfer and surface recombination processes.}, year = {1994} } @article{ author = {Lee, H. J. and Fermin, D. J. and Corn, R. M. and Girault, H. H.}, title = {Marangoni flow in micro-channels}, journal = {Electrochemistry Communications}, volume = {1}, number = {5}, pages = {190-193}, abstract = {A novel electrochemical method for driving fluids in micro-channels is presented. The principle is based upon the onset of Marangoni flow along the interface between an aqueous solution (mobile phase) and an organic electrolyte polymer gel coated on the inner walls of the microchannel. The gradient of surface tension responsible for the fluid motion arises from local changes in the surface charge. The excess charge is determined by the ionisation of surfactant species at the gel coating \ aqueous electrolyte interface which is effectively dependent on the Galvani potential difference. Potential differences of less than a volt between two closely spaced silver band electrodes along the microchannel can generate zones of high and low surface tension, promoting the motion of the aqueous electrolyte. (C) 1999 Elsevier Science S.A. All rights reserved.}, year = {1999} } @article{ author = {Lee, H. J. and Goodrich, T. T. and Corn, R. M.}, title = {SPR imaging measurements of 1-D and 2-D DNA microarrays created from microfluidic channels on gold thin films}, journal = {Analytical Chemistry}, volume = {73}, number = {22}, pages = {5525-5531}, year = {2001} } @article{ author = {Lee, H. J. and Li, Y. and Wark, A. W. and Corn, R. M.}, title = {Enzymatically amplified surface plasmon resonance imaging detection of DNA by exonuclease III digestion of DNA microarrays}, journal = {Analytical Chemistry}, volume = {77}, number = {16}, pages = {5096-5100}, year = {2005} } @article{ author = {Lee, H. J. and Nedelkov, D. and Corn, R. M.}, title = {Surface plasmon resonance imaging measurements of antibody arrays for the multiplexed detection of low molecular weight protein biomarkers}, journal = {Analytical Chemistry}, volume = {78}, number = {18}, pages = {6504-6510}, year = {2006} } @article{ author = {Lee, H. J. and Wark, A. and Corn, R. M.}, title = {Enzymatic manipulation of surface biomolecular nanostructures for the detection of bioaffinity interactions with SPR imaging and fluorescence measurements}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {231}, note = {231st National Meeting of the American-Chemical-Society MAR 26-30, 2006 Atlanta, GA}, year = {2006} } @article{ author = {Lee, H. J. and Wark, A. W. and Corn, R. M.}, title = {Creating advanced multifunctional biosensors with surface enzymatic transformations}, journal = {Langmuir}, volume = {22}, number = {12}, pages = {5241-5250}, year = {2006} } @article{ author = {Lee, H. J. and Wark, A. W. and Corn, R. M.}, title = {Utilizing ultrathin DNA/poly-lysine multilayer films to create liquid/liquid interfaces: spectroscopic characterization, interfacial reactions and nanoparticle adsorption}, journal = {Journal of Physics-Condensed Matter}, volume = {19}, year = {2007} } @article{ author = {Lee, H. J. and Wark, A. W. and Corn, R. M.}, title = {Enhanced bioaffinity sensing using surface plasmons, surface enzyme reactions, nanoparticles and diffraction gratings}, journal = {Analyst}, volume = {133}, number = {5}, pages = {596-601}, year = {2008} } @article{ author = {Lee, H. J. and Wark, A. W. and Corn, R. M.}, title = {Microarray methods for protein biomarker detection}, journal = {Analyst}, volume = {133}, number = {8}, pages = {975-983}, year = {2008} } @article{ author = {Lee, H. J. and Wark, A. W. and Goodrich, T. T. and Fang, S. P. and Corn, R. M.}, title = {Surface enzyme kinetics for biopolymer microarrays: a combination of Langmuir and Michaelis-Menten concepts}, journal = {Langmuir}, volume = {21}, number = {9}, pages = {4050-4057}, year = {2005} } @article{ author = {Lee, H. J. and Wark, A. W. and Li, Y. and Corn, R. M.}, title = {Fabricating RNA microarrays with RNA-DNA surface ligation chemistry}, journal = {Analytical Chemistry}, volume = {77}, number = {23}, pages = {7832-7837}, year = {2005} } @article{ author = {Lee, H. J. and Wegner, G. and Corn, R. M.}, title = {Spectroscopic and electrochemical characterization of biopolymer arrays at gold surfaces for biosensor applications}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {225}, pages = {U690-U690}, note = {225th National Meeting of the American-Chemical-Society MAR 23-27, 2003 NEW ORLEANS, LA}, year = {2003} } @article{ author = {Lee, H. J. and Yan, Y. L. and Marriott, G. and Corn, R. M.}, title = {Quantitative functional analysis of protein complexes on surfaces}, journal = {Journal of Physiology-London}, volume = {563}, number = {1}, pages = {61-71}, year = {2005} } @article{ author = {Li, M. and Lee, H. J. and Condon, A. E. and Corn, R. M.}, title = {DNA word design strategy for creating sets of non-interacting oligonucleotides for DNA microarrays}, journal = {Langmuir}, volume = {18}, number = {3}, pages = {805-812}, year = {2002} } @article{ author = {Li, Y. A. and Wark, A. W. and Lee, H. J. and Corn, R. M.}, title = {Single-nucleotide polymorphism genotyping by nanoparticle-enhanced surface plasmon resonance imaging measurements of surface ligation reactions}, journal = {Analytical Chemistry}, volume = {78}, number = {9}, pages = {3158-3164}, year = {2006} } @article{ author = {Li, Y. and Lee, H. J. and Corn, R. M.}, title = {Ultrasensitive SPR imaging sensors based on surface enzymatic reactions on nucleic acid microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {230}, pages = {U272-U272}, note = {230th National Meeting of the American-Chemical-Society AUG 28-SEP 01, 2005 Washington, DC}, year = {2005} } @article{ author = {Li, Y. and Lee, H. J. and Corn, R. M.}, title = {Fabrication and characterization of RNA aptamer microarrays for the study of protein-aptamer interactions with SPR imaging}, journal = {Nucleic Acids Research}, volume = {34}, number = {22}, pages = {6416-6424}, year = {2006} } @article{ author = {Li, Y. and Lee, H. J. and Corn, R. M.}, title = {Detection of protein biomarkers using RNA aptamer microarrays and enzymatically amplified surface plasmon resonance imaging}, journal = {Analytical Chemistry}, volume = {79}, number = {3}, pages = {1082-1088}, year = {2007} } @article{ author = {Liu, Q. H. and Frutos, A. G. and Thiel, A. J. and Corn, R. M. and Smith, L. M.}, title = {DNA computing on surfaces: Encoding information at the single base level}, journal = {Journal of Computational Biology}, volume = {5}, number = {2}, pages = {269-278}, abstract = {The feasibility of encoding a bit (0 or 1) of information for DNA-based computations at the single nucleotide level is evaluated, particularly with regard to the efficiency and specificity of hybridization discrimination. Hybridization experiments are performed on addressed arrays of 32 (2(5)) distinct oligonucleotides immobilized on chemically modified glass and gold surfaces,vith information encoded in a binary (base 2) format. Similar results are obtained oh both glass and gold surfaces and the results are generally consistent with thermodynamic calculations of matched and mismatched duplex stabilities, It is found that under the conditions required to obtain single nucleotide specificity in the hybridization process, hybridization efficiency is low, compromising the utility of single nucleotide encoding for DNA computing applications in the absence of some additional mechanism for increasing specificity. Several methods are suggested to provide such increased discrimination.}, year = {1998} } @article{ author = {Liu, Q. H. and Frutos, A. G. and Wang, L. M. and Thiel, T. J. and Gillmor, S. D. and Strother, C. T. and Condon, A. E. and Corn, R. M. and Lagally, M. G. and Smith, L. M.}, title = {Progress toward demonstration of a surface based DNA computation: a one word approach to solve a model satisfiability problem}, journal = {Biosystems}, volume = {52}, number = {1-3}, pages = {25-33}, note = {4th International Meeting on DNA Based Computers JUN 15-19, 1998 UNIV PENNSYLVANIA, PHILADELPHIA, PENNSYLVANIA}, abstract = {A multi-base encoding strategy is used in a one word approach to surface-based DNA computation. In this designed DNA model system, a set of 16 oligonucleotides, each a 16mer, is used with the format 5'-FFFFvvvvvvvvFFFF-3' in which 4-8 bits of data are stored in eight central variable ('v') base locations, and the remaining fixed ('F') base locations are used as a word label. The detailed implementations are reported here. In order to achieve perfect discrimination between each oligonucleotide, the efficiency and specificity of hybridization discrimination of the set of 16 oligonucleotides were examined by carrying out the hybridization of each individual fluorescently tagged complement to an array of 16 addressed immobilized oligonucleotides. A series of preliminary hybridization experiments are presented and further studies about hybridization, enzymatic destruction, read out and demonstrations of a SAT problem are forthcoming. (C) 1999 Elsevier Science Ireland Ltd. All rights reserved.}, year = {1999} } @article{ author = {Liu, Q. H. and Wang, L. M. and Frutos, A. G. and Condon, A. E. and Corn, R. M. and Smith, L. M.}, title = {DNA computing on surfaces}, journal = {Nature}, volume = {403}, number = {6766}, pages = {175-179}, abstract = {DNA computing was proposed(1) as a means of solving a class of intractable computational problems in which the computing time can grow exponentially with problem size (the 'NP-complete' or non-deterministic polynomial time complete problems). The principle of the technique has been demonstrated experimentally for a simple example of the hamiltonian path problem(2) (in this case, finding an airline flight path between several cities, such that each city is visited only once(3)). DNA computational approaches to the solution of other problems have also been investigated(4-9). One technique(10-13) involves the immobilization and manipulation of combinatorial mixtures of DNA on a support. A set of DNA molecules encoding all candidate solutions to the computational problem of interest is synthesized and attached to the surface. Successive cycles of hybridization operations and exonuclease digestion are used to identify and eliminate those members of the set that are not solutions. Upon completion of all the multistep cycles, the solution to the computational problem is identified using a polymerase chain reaction to amplify the remaining molecules, which are then hybridized to an addressed array. The advantages of this approach are its scalability and potential to be automated (the use of solid-phase formats simplifies the complex repetitive chemical processes, as has been demonstrated in DNA and protein synthesis(14)). Here we report the use of this method to solve a NP-complete problem. We consider a small example of the satisfiability problem (SAT)(2), in which the values of a set of boolean variables satisfying certain logical constraints are determined.}, year = {2000} } @article{ author = {Lockett, M. R. and Weibel, S. C. and Phillips, M. F. and Shortreed, M. R. and Sun, B. and Corn, R. M. and Hamers, R. J. and Cerrina, F. and Smith, L. M.}, title = {Carbon-on-metal films for surface plasmon resonance detection of DNA arrays}, journal = {Journal of the American Chemical Society}, volume = {130}, number = {27}, pages = {8611-+}, year = {2008} } @article{ author = {Lynch, M. L. and Barner, B. J. and Corn, R. M.}, title = {INSITU 2ND HARMONIC-GENERATION STUDIES OF CHEMISORPTION AT WELL-ORDERED PT(111) ELECTRODES IN PERCHLORIC-ACID SOLUTIONS}, journal = {Journal of Electroanalytical Chemistry}, volume = {300}, number = {1-2}, pages = {447-465}, abstract = {The technique of optical second harmonic generation (SHG) is used an in situ probe of chemisorption and structure at flame-annealed Pt(111) electrodes in perchloric acid solutions. Rotational anisotropy SHG measurements demonstrate that the single crystal surface order is preserved when the electrodes are transferred to solution with an iodine overlayer and cleaned through an iodine-CO exchange reaction and subsequent CO oxidation electrochemistry. The chemisorption of both iodine and CO produces an anisotropic response from the surface with a reduced average surface symmetry due to the presence of the adsorbed overlayer. The SHG signal from the well-ordered Pt(111) surface in perchloric acid after the removal of the CO also reveals the presence of an ordered chemisorbed overlayer at all electrode potentials negative of the butterfly peaks. Although the identity of the chemisorbed species cannot be determined unambiguously from the SHG measurements, comparisons with the potential dependent SHG response from Pt(100) and polycrystalline platinum electrodes relate the SHG signal in this potential range to an ordered overlayer of a hydrogen species. The SHG measurements also confirm the electrochemical evidence that these ordered structures are modified upon the disruption of the longer range domain structure of the well-ordered Pt(111) surface.}, year = {1991} } @article{ author = {Lynch, M. L. and Barner, B. J. and Lantz, J. M. and Corn, R. M.}, title = {INSITU 2ND HARMONIC-GENERATION STUDIES OF BISULFATE ADSORPTION AT WELL-ORDERED PT(111) AND PT(100) ELECTRODES}, journal = {Journal De Chimie Physique Et De Physico-Chimie Biologique}, volume = {88}, number = {7-8}, pages = {1271-1289}, abstract = {The technique of optical second harmonic generation (SHG) is used to monitor bisulfate chemisorption at well-ordered Pt(111) and Pt(100) electrodes in perchloric acid media. A comparison of the surface SHG response from the well-ordered single crystal electrodes to that obtained from polycrystalline platinum electrodes indicates that at potentials positive of hydrogen adsorption a limited amount of bisulfate chemisorption inhibits and suppresses the other electrochemical surface reactions. Upon disordering, the amount of bisulfate chemisorption increases towards the levels observed at polycrystalline surfaces.}, year = {1991} } @article{ author = {Lynch, M. L. and Corn, R. M.}, title = {INSITU 2ND-HARMONIC GENERATION STUDIES OF THE SURFACE-STRUCTURE OF A WELL-ORDERED PT(111) ELECTRODE}, journal = {Journal of Physical Chemistry}, volume = {94}, number = {11}, pages = {4382-4385}, year = {1990} } @article{ author = {Lynch, M. L. and Corn, R. M.}, title = {SURFACE PHASE-TRANSITION OF ORDERED IODINE MONOLAYERS ON A PT(111) ELECTRODE AS STUDIED BY NORMAL INCIDENCE OPTICAL 2ND HARMONIC-GENERATION}, journal = {Journal of Electroanalytical Chemistry}, volume = {318}, number = {1-2}, pages = {379-386}, year = {1991} } @article{ author = {Marathe, A. and Condon, A. E. and Corn, R. M.}, title = {On combinatorial DNA word design}, journal = {Journal of Computational Biology}, volume = {8}, number = {3}, pages = {201-219}, year = {2001} } @article{ author = {Naujok, R. R. and Duevel, R. V. and Corn, R. M.}, title = {FLUORESCENCE AND FOURIER-TRANSFORM SURFACE-ENHANCED RAMAN-SCATTERING MEASUREMENTS OF METHYLENE-BLUE ADSORBED ONTO A SULFUR-MODIFIED GOLD ELECTRODE}, journal = {Langmuir}, volume = {9}, number = {7}, pages = {1771-1774}, abstract = {Surface enhanced Raman scattering (SERS) and molecular fluorescence are used to probe the structure of a methylene blue monolayer adsorbed onto a sulfur-modified polycrystalline gold electrode. Changes in the wavelength of fluorescence for methylene blue on the gold electrode as compared to dilute solution indicate that the dye molecules' state of aggregation and electronic structure have been modified upon adsorption to the surface. An increase in the molecular fluorescence is observed on the sulfur-modified gold electrodes, and is attributed to the intervention of the sulfur between the methylene blue and the metal surface. To avoid interference from the methylene blue fluorescence, ex situ SERS spectra were obtained with a Fourier transform (FT) spectrometer that utilized an excitation wavelength of 1064 nm. The FT-SERS spectra from methylene blue on sulfur-modified and bare gold surfaces exhibit differences that can be ascribed to the interactions of the dye molecules with the sulfur monolayer.}, year = {1993} } @article{ author = {Naujok, R. R. and Higgins, D. A. and Hanken, D. G. and Corn, R. M.}, title = {OPTICAL 2ND-HARMONIC GENERATION MEASUREMENTS OF MOLECULAR ADSORPTION AND ORIENTATION AT THE LIQUID-LIQUID ELECTROCHEMICAL INTERFACE}, journal = {Journal of the Chemical Society-Faraday Transactions}, volume = {91}, number = {10}, pages = {1411-1420}, abstract = {The surface-sensitive spectroscopic technique of optical second-harmonic generation (SHG) is applied to the in situ study of molecular adsorption at the interface between two immiscible electrolyte solutions (ITIES). The resonant SHG from molecules which exhibit a large non-linear optical response at a specific wavelength can be used to measure the relative surface coverage of surfactants at the ITIES as a function of the external electrochemical parameters. In addition, the polarization dependence of the resonant surface SHG can be used to estimate the average molecular orientation of adsorbates at the liquid/liquid electrochemical interface. As an example, the adsorption of the surfactant 4-(4'-dodecyloxyazobenzene)benzoic acid at the water/1,2-dichloroethane interface is characterized as a function of applied potential, surfactant concentration and aqueous pH with in situ resonant molecular SHG measurements. An analysis of the SHG data results in the determination of the local potential and surface pH experienced by the surfactant.}, year = {1995} } @article{ author = {Naujok, R. R. and Higgins, D. A. and Hanken, D. G. and Corn, R. M.}, title = {OPTICAL 2ND-HARMONIC GENERATION MEASUREMENTS OF MOLECULAR ADSORPTION AND ORIENTATION AT THE LIQUID-LIQUID ELECTROCHEMICAL INTERFACE (VOL 91, PG 1411, 1995)}, journal = {Journal of the Chemical Society-Faraday Transactions}, volume = {91}, number = {15}, pages = {2353-2353}, year = {1995} } @article{ author = {Naujok, R. R. and Paul, H. J. and Corn, R. M.}, title = {Optical second harmonic generation studies of azobenzene surfactant adsorption and photochemistry at the water/1,2-dichloroethane interface}, journal = {Journal of Physical Chemistry}, volume = {100}, number = {25}, pages = {10497-10507}, abstract = {The surface-sensitive spectroscopic technique of optical second harmonic generation (SHG) is employed to study the adsorption and photochemistry of surfactant molecules at the water/1,2-dichloroethane (DCE) interface. Resonant SHG measurements at 730 nm are used to monitor the adsorption of the azobenzene surfactant 4-[[(dodecyloxy)benz-4-yl]azo]benzoic acid (DBA) from DCE solution to the interface at an aqueous pH of 8 or greater. The concentration and pH dependence of the resonant SHG from the adsorbed monolayer indicates that the DBA exists in its anionic (carboxylate) form at the interface. In a series of combined photochemical/SHG experiments the trans/cis photoisomerization of the adsorbed DBA anions is examined. SHG measurements demonstrate that illumination of the surface with light at 365 nm converts the adsorbed trans-DBA molecules to the cis isomer. The cis-DBA anion is found to be unusually stable at the liquid/liquid interface, and the entire photoactive monolayer (total area 4 cm(2)) can be photochemically converted in approximately 450 s with an illumination spot of 0.12 cm(2). This relatively short conversion time is attributed to surface-tension-induced convection effects that occur during the photochemical conversion of the monolayer. Illumination of the cis-DBA anions with light at 440 nm reconverts the entire surfactant monolayer back to the trans-DBA form in the same time frame.}, year = {1996} } @article{ author = {Nelson, B. P. and Candal, R. and Corn, R. M. and Anderson, M. A.}, title = {Control of surface and zeta potentials on nanoporous TiO2 films by potential-determining and specifically adsorbed ions}, journal = {Langmuir}, volume = {16}, number = {15}, pages = {6094-6101}, year = {2000} } @article{ author = {Nelson, B. P. and Frutos, A. G. and Brockman, J. M. and Corn, R. M.}, title = {Near-infrared surface plasmon resonance measurements of ultrathin films. 1. Angle shift and SPR imaging experiments}, journal = {Analytical Chemistry}, volume = {71}, number = {18}, pages = {3928-3934}, abstract = {The application of surface plasmon resonance (SPR) measurements to the study of ultrathin organic and inorganic films adsorbed onto gold surfaces utilizing near-infrared (NIR) excitation from 800 to 1152 mn is described. SPR scanning angle measurements of film thickness are demonstrated at 814 and 1152 nm using low-power diode and HeNe laser sources, respectively. Several advantages of SPR in the NIR are noted. The in situ reflectivity versus angle of incidence curves sharpen greatly (as compared to 632.8 nm) at longer wavelengths so that there is no loss in sensitivity in the measurement of film thickness despite a doubling of the excitation wavelength. The sharper resonance and longer wavelengths also allow for the measurement of thicker films. Examples of SPR thickness measurements for self-assembled alkanethiol monolayers and composite biopolymer/SiO2 nanoparticle electrostatic multilayer films are given. SPR imaging experiments are also performed at various NIR wavelengths using an incoherent white light source and narrow band-pass filters. The incoherent white light source eliminates laser fringes that have been observed in previous SPR imaging experiments, and the use of narrow band-pass filters allows for the easy selection and variation of excitation wavelength. The narrowness of the reflectivity versus angle curves leads to greater contrast in NIR SPR images compared to the same features examined with excitation from visible light. The combination of these changes results in nearly 1 order of magnitude enhancement in the SPR differential reflectivity image, indicating that SPR imaging is best conducted with incoherent NIR excitation. One disadvantage of using NIR wavelengths for SPR imaging is that the surface plasmon propagation length increases in the NIR so that the lateral image resolution is reduced; however, image features larger than 50 mu m can easily be resolved. A NIR SPR image of a DNA array onto which single-stranded DNA binding protein has bound is shown as an example of how NIR SPR imaging experiments have sufficient sensitivity to monitor DNA-protein interactions.}, year = {1999} } @article{ author = {Nelson, B. P. and Grimsrud, T. E. and Liles, M. R. and Goodman, R. M. and Corn, R. M.}, title = {Surface plasmon resonance imaging measurements of DNA and RNA hybridization adsorption onto DNA microarrays}, journal = {Analytical Chemistry}, volume = {73}, number = {1}, pages = {1-7}, year = {2001} } @article{ author = {Nelson, B. P. and Liles, M. R. and Frederick, K. B. and Corn, R. M. and Goodman, R. M.}, title = {Label-free detection of 16S ribosomal RNA hybridization on reusable DNA arrays using surface plasmon resonance imaging}, journal = {Environmental Microbiology}, volume = {4}, number = {11}, pages = {735-743}, year = {2002} } @article{ author = {Paul, H. J. and Corn, R. M.}, title = {Second-harmonic generation measurements of electrostatic biopolymer-surfactant coadsorption at the water/1,2-dichloroethane interface}, journal = {Journal of Physical Chemistry B}, volume = {101}, number = {23}, pages = {4494-4497}, abstract = {The electrostatic coadsorption of the synthetic polypeptide poly-L-glutamic acid (pGlu) and the cationic hemicyanine surfactant trans-4-[4-(dibutylamino)styryl]-1-methylpyridinium iodide (D+-CH3) is observed at the water/1,2-dichloroethane (DCE) interface with the spectroscopic technique of optical second-harmonic generation (SHG). The adsorption isotherm of D+-CH3 to the water/DCE interface is obtained with a combination of resonant surface SHG and interfacial tension measurements. In the presence of polyanionic pGlu in the aqueous phase at a pH of 8.5, the limiting surface coverage of the cationic surfactant is enhanced by a factor of 3.7. In contrast, no such enhancement is observed in the presence of p6lu for the adsorption of the neutral zwitterionic hemicyanine surfactant trans-4-[4-(dibutylamino)styryl]-1-(3-sulfopropyl)pyridinium hydroxide inner salt hydrate (D+-(CH2)(3)-SO3-) to the water/DCE interface, Additionally, no enhancement in surfactant adsorption is observed for D+-CH3 when the pGlu in the aqueous phase is replaced with a solution of the monomer L-glutamic acid. These observations demonstrate that the coadsorption of pGlu and D+-CH3 is a multipoint electrostatic adsorption interaction at the water/DCE interface.}, year = {1997} } @article{ author = {Saez, E. I. and Corn, R. M.}, title = {IN-SITU POLARIZATION MODULATION-FOURIER TRANSFORM-INFRARED SPECTROELECTROCHEMISTRY OF PHENAZINE AND PHENOTHIAZINE DYE FILMS AT POLYCRYSTALLINE GOLD ELECTRODES}, journal = {Electrochimica Acta}, volume = {38}, number = {12}, pages = {1619-1625}, abstract = {Polarization modulation-Fourier transform infrared (PM-FTir) spectra were obtained in situ for polymer films of neutral red and thionine, and for a film of leucomethylene blue generated on a gold electrode as a function of potential. The spectra of the polymer films revealed that the aromatic rings lie mostly parallel to the electrode surface in both the reduced and oxidized forms. In contrast, the spectrum of the adsorbed leuco methylene blue film indicated that most of the molecules within the film are oriented perpendicular to the gold surface.}, year = {1993} } @article{ author = {Sato, Y. and Frey, B. L. and Corn, R. M. and Uosaki, K.}, title = {POLARIZATION MODULATION FOURIER-TRANSFORM INFRARED STUDIES OF THE EFFECTS OF SELF-ASSEMBLY TIME ON THE ORDER AND ORIENTATION OF 11-FERROCENYL-1-UNDECANETHIOL MONOLAYERS ON GOLD}, journal = {Bulletin of the Chemical Society of Japan}, volume = {67}, number = {1}, pages = {21-25}, abstract = {The effects of self-assembly time on the order and orientation of 11-ferrocenyl-1-undecanethiol (FcC(11)SH) molecular layers on gold were studied with polarization modulation Fourier transform infrared spectroscopy. A comparison between the intensity of the asymmetric methylene stretching mode of a 1-octadecanethiol monolayer and that of the FcC(11)SH molecular layer confirmed that the FcC(11)SH molecules formed a self-assembled monolayer on the gold surface. The conformational order of the monolayer increased with longer self-assembly time as evidenced by a decrease in the vibrational frequencies of the methylene stretching modes and a decrease in the full width at half maximum of these bands. The peak area of the asymmetric methylene stretch also decreased with longer self-assembly time, implying that the FcC(11)SH molecules stood more erect with respect to the gold surface as the monolayer self-assembled.}, year = {1994} } @article{ author = {Smith, E. A. and Corn, R. M.}, title = {Surface plasmon resonance imaging as a tool to monitor biomolecular interactions in an array based format}, journal = {Applied Spectroscopy}, volume = {57}, number = {11}, pages = {320A-332A}, year = {2003} } @article{ author = {Smith, E. A. and Erickson, M. G. and Ulijasz, A. T. and Weisblum, B. and Corn, R. M.}, title = {Surface plasmon resonance imaging of transcription factor proteins: Interactions of bacterial response regulators with DNA arrays on gold films}, journal = {Langmuir}, volume = {19}, number = {5}, pages = {1486-1492}, year = {2003} } @article{ author = {Smith, E. A. and Kyo, M. and Kumasawa, H. and Nakatani, K. and Saito, I. and Corn, R. M.}, title = {Chemically induced hairpin formation in DNA monolayers}, journal = {Journal of the American Chemical Society}, volume = {124}, number = {24}, pages = {6810-6811}, year = {2002} } @article{ author = {Smith, E. A. and Thomas, W. D. and Kiessling, L. L. and Corn, R. M.}, title = {Surface plasmon resonance imaging studies of protein-carbohydrate interactions}, journal = {Journal of the American Chemical Society}, volume = {125}, number = {20}, pages = {6140-6148}, year = {2003} } @article{ author = {Smith, E. A. and Wanat, M. J. and Cheng, Y. F. and Barreira, S. V. P. and Frutos, A. G. and Corn, R. M.}, title = {Formation, spectroscopic characterization, and application of sulfhydryl-terminated alkanethiol monolayers for the chemical attachment of DNA onto gold surfaces}, journal = {Langmuir}, volume = {17}, number = {8}, pages = {2502-2507}, year = {2001} } @article{ author = {Smith, E. A. and Wegner, G. J. and Lee, H. J. and Corn, R. M.}, title = {SPR imaging measurements of protein adsorption onto carbohydrate and peptide microarrays}, journal = {Abstracts of Papers of the American Chemical Society}, volume = {224}, pages = {U455-U455}, note = {1}, year = {2002} } @article{ author = {Smith, L. M. and Corn, R. M. and Condon, A. E. and Lagally, M. G. and Frutos, A. G. and Liu, Q. H. and Thiel, A. J.}, title = {A surface-based approach to DNA computation}, journal = {Journal of Computational Biology}, volume = {5}, number = {2}, pages = {255-267}, abstract = {A scalable approach to DNA-based computations is described. Complex combinatorial mixtures of DNA molecules encoding all possible answers to a computational problem are synthesized and attached to the surface of a solid support. This set of molecules is queried in successive MARK (hybridization) and DESTROY (enzymatic digestion) operations. Determination of the sequence of the DNA molecules remaining on the surface after completion of these operations yields the answer to the computational problem. Experimental demonstrations of aspects of the strategy are presented.}, year = {1998} } @article{ author = {Thiel, A. J. and Frutos, A. G. and Jordan, C. E. and Corn, R. M. and Smith, L. M.}, title = {In situ surface plasmon resonance imaging detection of DNA hybridization to oligonucleotide arrays on gold surfaces}, journal = {Analytical Chemistry}, volume = {69}, number = {24}, pages = {4948-4956}, abstract = {A new method for constructing oligonucleotide arrays on gold surfaces has been developed, and these arrays have been used in DNA hybridization experiments with in situ surface plasmon resonance (SPR) imaging detection. The detection technique was able to differentiate between single-and double-stranded DNA regions on the gold surface. The hybridization of both oligonucleotides and PCR-amplified DNA fragments was detectable, with the latter exhibiting slower hybridization kinetics. Temperature control of the in situ SPR cell was used to discriminate between perfectly matched duplexes and single-base-mismatched duplexes. The SPR detection technique requires no label on the DNA, but fluorescently labeled targets were also tested and detected by fluorescence imaging as an independent verification of the hybridization behavior of these DNA arrays, The in situ SPR imaging method for detection of DNA hybridization is expected to complement other existing methods for study of DNA interactions and might find future uses in mutation screening assays and DNA resequencing.}, year = {1997} } @article{ author = {Toman, J. J. and Corn, R. M. and Brown, S. D.}, title = {CONVOLUTION VOLTAMMETRY OF METAL-COMPLEXES}, journal = {Analytica Chimica Acta}, volume = {123}, number = {JAN}, pages = {187-199}, year = {1981} } @article{ author = {Wang, L. M. and Liu, Q. H. and Corn, R. M. and Condon, A. E. and Smith, L. M.}, title = {Multiple word DNA computing on surfaces}, journal = {Journal of the American Chemical Society}, volume = {122}, number = {31}, pages = {7435-7440}, year = {2000} } @article{ author = {Wang, L. M. and Liu, Q. H. and Frutos, A. G. and Gillmor, S. D. and Thiel, A. J. and Strother, T. C. and Condon, A. E. and Corn, R. M. and Lagally, M. G. and Smith, L. M.}, title = {Surface-based DNA computing operations: DESTROY and READOUT}, journal = {Biosystems}, volume = {52}, number = {1-3}, pages = {189-191}, note = {4th International Meeting on DNA Based Computers JUN 15-19, 1998 UNIV PENNSYLVANIA, PHILADELPHIA, PENNSYLVANIA}, abstract = {DNA computing on surfaces is where complex combinatorial mixtures of DNA molecules are immobilized on a substrate and subsets are tagged and enzymatically modified (DESTROY) in repeated cycles of the DNA computation. A restriction enzyme has been chosen for the surface DESTROY operation. For the READOUT operation, both cycle sequencing and PCR amplification followed by addressed array hybridization were studied to determine the DNA sequences after the computations. (C) 1999 Elsevier Science Ireland Ltd. All rights reserved.}, year = {1999} } @article{ author = {Wark, A. W. and Lee, H. J. and Corn, R. M.}, title = {Long-range surface plasmon resonance imaging for bioaffinity sensors}, journal = {Analytical Chemistry}, volume = {77}, number = {13}, pages = {3904-3907}, year = {2005} } @article{ author = {Wark, A. W. and Lee, H. J. and Corn, R. M.}, title = {Multiplexed detection methods for profiling microRNA expression in biological samples}, journal = {Angewandte Chemie-International Edition}, volume = {47}, number = {4}, pages = {644-652}, year = {2008} } @article{ author = {Wark, A. W. and Lee, H. J. and Qavi, A. J. and Corn, R. M.}, title = {Nanoparticle-enhanced diffraction gratings for ultrasensitive surface plasmon biosensing}, journal = {Analytical Chemistry}, volume = {79}, number = {17}, pages = {6697-6701}, year = {2007} } @article{ author = {Wegner, G. J. and Lee, H. J. and Corn, R. M.}, title = {Characterization and optimization of peptide arrays for the study of epitope-antibody interactions using surface plasmon resonance imaging}, journal = {Analytical Chemistry}, volume = {74}, number = {20}, pages = {5161-5168}, year = {2002} } @article{ author = {Wegner, G. J. and Lee, N. J. and Marriott, G. and Corn, R. M.}, title = {Fabrication of histidine-tagged fusion protein arrays for surface plasmon resonance imaging studies of protein-protein and protein-DNA interactions}, journal = {Analytical Chemistry}, volume = {75}, number = {18}, pages = {4740-4746}, year = {2003} } @article{ author = {Wegner, G. J. and Wark, A. W. and Lee, H. J. and Codner, E. and Saeki, T. and Fang, S. P. and Corn, R. M.}, title = {Real-time surface plasmon resonance imaging measurements for the multiplexed determination of protein adsorption/desorption kinetics and surface enzymatic reactions on peptide microarrays}, journal = {Analytical Chemistry}, volume = {76}, number = {19}, pages = {5677-5684}, year = {2004} } @article{ author = {Yagi, I. and Lantz, J. M. and Nakabayashi, S. and Corn, R. M. and Uosaki, K.}, title = {In situ optical second harmonic generation studies of electrochemical deposition of tellurium on polycrystalline gold electrodes}, journal = {Journal of Electroanalytical Chemistry}, volume = {401}, number = {1-2}, pages = {95-101}, abstract = {The electrodeposition of tellurium (Te) on polycrystalline gold electrodes was studied using in situ optical second harmonic generation (SHG) at two different excitation wavelengths. On excitation at 1064 nm, the SH signal decreased dramatically with the first Te underpotential deposition (upd) and increased slightly with the second upd and the bulk deposition of Te. There was a linear correlation between the square root of the SH intensity from the surface and the surface coverage of Te, although the proportionality constant of this correlation for the first Te upd was different from those for the second upd and bulk deposition. This is possibly because of the stronger interaction of the first upd layer of Te than the second and bulk layer of Te with the substrate surface. However, on excitation at 585 nm, the behavior of the SH signal was more complicated, especially during the desorption process of the first Te monolayer. An increase in the SH intensity was observed with the first Te upd, but this increase in SHG still continued in the potential region in which no deposition of Te occurred. These results are interpreted by considering the existence of an optical resonance at the Au surface covered with a Te monolayer.}, year = {1996} } @article{ author = {Zadoyan, R. and Seferyan, H. Y. and Wark, A. W. and Corn, R. M. and Apkarian, V. A.}, title = {Interfacial velocity-dependent plasmon damping in colloidal metallic nanoparticles}, journal = {Journal of Physical Chemistry C}, volume = {111}, number = {29}, pages = {10836-10840}, year = {2007} }