Alice Deckert - Academia.edu (original) (raw)

Papers by Alice Deckert

Journal of The Optical Society of America B-optical Physics, 1986

The Journal of Physical Chemistry B, 2013

Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-pa... more Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-path intermediates are shown to involve unimolecular and, in one case, bimolecular structure in one of the single strands of complementary DNA. Three models are developed to account for the observed single-stranded structures that are formed in parallel with duplex formation. These models are applied to the analysis of stopped-flow data for eight different nonself-complementary duplex formation reactions in order to extract the elementary rate constant for formation of the duplex from the complementary random coil single-stranded DNA. The free energy of activation (at 25 °C) for the denaturation of each duplex is calculated from these data and is shown to have a linear correlation to the overall standard free energy for duplex formation (also at 25 °C). Duplexes that contain mismatches obey a parallel linear free-energy (LFE) relationship with a y-intercept that is greater than that of duplexes without mismatches. Slopes near unity for the LFE relationships indicate that all duplexes go through an early, unstructured transition state.

The Journal of Physical Chemistry B, 2004

Langmuir, 1999

Synthesis of Docosyl Mesylate. The docosyl mesylate was prepared from 1-docosanol and excess meth... more Synthesis of Docosyl Mesylate. The docosyl mesylate was prepared from 1-docosanol and excess methyl sulfonyl chloride. A 5 g mass of 1-docosanol was placed in a 250 mL three-necked flask fitted with a dropping funnel, a drying tube, and a condenser. Approximately 50 mL of ...

Surface Science Letters

Reaction and desorption are competing surface processes and their product yields are dependent up... more Reaction and desorption are competing surface processes and their product yields are dependent upon both the surface heating rate and the kinetic parameters for reaction and desorption. Laser induced thermal desorption (LITD) is a useful probe of surface reactions because the desorption yield can often dominate the reaction yield at rapid laser induced heating rates. In this Letter, the relationship between the product yields for desorption and reaction as a function of surface heating rate was investigated numerically because an analytical equation does not exist. An empirical equation was determined that presents the functional relationship between the surface heating rate at which the product yields for reaction and desorption are 1 : 1 and the kinetic parameters for reaction and desorption. This equation is useful for predicting the experimental heating rates required for LITD studies of surface reaction kinetics.

Langmuir, 1994

... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and... more ... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and Terry Encalarde Department of Chemistry, College of the Holy Cross, Worcester, Massachusettes 01610 ... (26) Fischetti, RF; Filipkowski, M.; Gerito, A. F.; Blasie, JK Phys. ...

Langmuir, 1994

... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and... more ... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and Terry Encalarde Department of Chemistry, College of the Holy Cross, Worcester, Massachusettes 01610 ... (26) Fischetti, RF; Filipkowski, M.; Gerito, A. F.; Blasie, JK Phys. ...

Langmuir, 1995

The first study of the polymerization and thermochromism in Langmuir-Blodgett films of the Cd2+ s... more The first study of the polymerization and thermochromism in Langmuir-Blodgett films of the Cd2+ salts of 5,7-docosadiynoic acid (DCDA) and 5,7-tretracosadiynoic acid (TTCDA) formed at molecular areas of 22 and 26 A2/molecule is reported. The polymerization behavior and ...

The Journal of Chemical Physics, 1988

ABSTRACT

The Journal of Chemical Physics, 1987

The decomposition reaction of methanol on Ru(001) was studied using laser induced thermal desorpt... more The decomposition reaction of methanol on Ru(001) was studied using laser induced thermal desorption (LITD). The LITD studies, combined with temperature programmed desorption and Auger electron spectroscopy measurements, allowed absolute product yields for the three competing surface pathways to be determined over the entire range of chemisorbed methanol coverages at a heating rate of β=2.6 K/s. At the lowest methanol coverages of θ≤0.07θs, where θs is the surface coverage of a saturated chemisorbed layer, all the methanol reacted between 220–280 K. This methanol decomposition reaction yielded desorption-limited H2 and CO as reaction products. At higher coverages, molecular desorption and the second methanol decomposition reaction involving C–O bond breakage became increasingly important. At θ=θs, 50% of the initial methanol coverage desorbed, 24% produced H2 and CO and 26% left C on the surface. Isothermal LITD kinetic measurements were carried out at low methanol coverages of θ≤0.07θs at various temperatures from 180 to 220 K. The initial decomposition rates obtained from the isothermal LITD studies displayed first order kinetics. The decomposition kinetics at later times could not be fit by first order kinetics and suggested a self-poisoned reaction. Subsequent LITD studies revealed that CO inhibited the decomposition reaction. The product CO inhibition was modeled by first order kinetics with a CO-coverage dependent activation barrier. The observed first order reaction kinetics at low methanol coverage could be expressed by the pre-exponential ν=106 s−1 and the coverage-dependent activation barrier E=7 kcal/mol+αθCO/θCO,s, where α=20 kcal/mol and θCO/θCO,s is the dimensionless CO coverage normalized to the CO saturation coverage θCO,s. Isotopic LITD studies revealed that the decomposition kinetics of CH3OH, CD3OH, and CH3OD were identical. This equivalence suggested that the hindered rotation of the surface methoxy species is the reaction coordinate for the rate-limiting step in the decomposition reaction.

The Journal of Chemical Physics, 1986

ABSTRACT

Journal of Chemical Education, 1998

... Physical Chemistry Laboratory Course Alice A. Deckert* and Lisa P. Nestor Department of Chemi... more ... Physical Chemistry Laboratory Course Alice A. Deckert* and Lisa P. Nestor Department of Chemistry, College of Holy Cross, Worcester, MA 01610 Donna DiLullo Department of Biology and Chemistry, Springfield College, Springrfield, MA 01109-3797 ... 22. Bodner, CM J. Chem. ...

Langmuir, 2002

The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexadecylt... more The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexadecylthiomethylbenzenes where X was a mesylate, chloride, or bromide was investigated using surface plasmon resonance (spr). The data were fit to a model in which nonspecific adsorption competes with a ...

Biochemistry, 2013

The rates of duplex formation for two octamers of DNA (5&... more The rates of duplex formation for two octamers of DNA (5' d-CACGGCTC/5' d-GAGCCGTG and 5' d-CACAGCAC/5' d-GTGCTGTG), the homologous RNA, and both sets of hybrids in 1 M NaCl buffer have been measured using stopped-flow spectroscopy. In addition, the thermodynamic parameters, ΔH° and ΔS°, have been determined for the same sequences under the same buffer conditions using optical melting techniques. These data reveal a linear free energy relationship between the free energy of activation for denaturation and the change in free energy for formation of the duplexes. This relationship indicates that these duplex formation reactions occur through a common unstructured transition state that is more similar to the single strands in solution than to the ensuing duplex. In addition, these data confirm that the greater stability of RNA duplexes relative to that of homologous DNA and hybrid duplexes is controlled by the denaturation rate and not the duplex formation rate.

The rates of duplex formation for two octamers of DNA (5′ d-CACGGCTC/5′ d-GAGCCGTG and 5′ d-CACAG... more The rates of duplex formation for two octamers of DNA (5′ d-CACGGCTC/5′ d-GAGCCGTG and 5′ d-CACAGCAC/5′ d-GTGCTGTG), the homologous RNA, and both sets of hybrids in 1 M NaCl buffer have been measured using stopped-flow spectroscopy. In addition, the thermodynamic parameters, ΔH° and ΔS°, have been determined for the same sequences under the same buffer conditions using optical melting techniques. These data reveal a linear free energy relationship between the free energy of activation for denaturation and the change in free energy for formation of the duplexes. This relationship indicates that these duplex formation reactions occur through a common unstructured transition state that is more similar to the single strands in solution than to the ensuing duplex. In addition, these data confirm that the greater stability of RNA duplexes relative to that of homologous DNA and hybrid duplexes is controlled by the denaturation rate and not the duplex formation rate. D uplex formation of nucleic acids is one of the most fundamental biological processes. RNA primers form a duplex with the parental strand DNA during replication. 1 Codon versus anticodon recognition requires the formation of a short stretch of duplex during translation. 2 SiRNAs, miRNAs, and piwiRNAs all form duplexes with their target sequences. 3−5 In addition, laboratory techniques such as polymerase chain reaction rely on duplex formation to complete a round of amplification. Therefore, understanding the molecular details of duplex formation will greatly facilitate our understanding of many processes central to the biology of the cell. The stability of nucleic acid duplexes has been investigated by multiple laboratories. 6−11 These results have led to the development of the nearest-neighbor model for predicting the stability of nucleic acid duplexes that takes into account the strength of H-bonding and base-stacking interactions. While there is some sequence specificity, in general RNA duplexes have been found to be more stable than either the DNA or DNA−RNA hybrid duplexes with similar sequences. 6−8 These models can generally predict the stability of duplexes to within approximately 0.5 kcal/mol or within a 2-fold range of the binding constant, but the underlying reason for the relative stability of the RNA duplexes is not well understood. A full understanding of the relative stability of homologous RNA and DNA duplexes can be obtained only by measuring both the equilibrium and kinetic parameters for the duplex formation equilibria under the same solvent conditions. Several early studies of the kinetics of duplex formation have led investigators to speculate that the stability of nucleic acid duplexes is controlled by the denaturation, or " off " , rate because the measured duplex formation, or " on " , rate constants tend to be similar regardless of sequence. 12 However, this speculation has not yet been rigorously tested. The base-by-base mechanism first proposed by Wetmur and Davidson 13 is the typical starting point for the interpretation of kinetic data. This mechanism has often been characterized in terms of a nucleation step followed by a fast zipping of the remaining base pairs. The first, rate-determining nucleation step takes single-stranded DNA or RNA to a nucleated duplex with two to four 14−16 H-bonded and stacked bases. Although most sources agree that only a few H-bonded bases exist in the nucleated intermediate, the number of base pairs that must align at the transition state has been estimated by Manning and others to be much higher, 15 or 16 bases. 17−19 This nucleation step is followed by a rapid zipping step in which the rest of the duplex base stacks and hydrogen bonds. Each of these steps most likely consists of individual base-by-base steps that cannot be distinguished and are thus treated as an ensemble or kinetic cluster. 20 In the steady state limit of this model, the nucleated intermediate is not kinetically significant, and this model correlates with the two-state model generally used to obtain thermodynamic parameters from melting data. In this limit, the on and off rate constants can be assigned to the formation and denaturation, respectively, of the nucleation site, which is rate-limiting. In contrast to the large thermodynamic data set for nucleic acid duplex formation found in the literature, the kinetic data set is much smaller. Whereas most thermodynamic studies have been conducted using the same solvent system (1 M NaCl), the existing kinetic data have been obtained under a variety of solvent conditions, making the correlation of these kinetic data with thermodynamic data difficult. Furthermore, the values of overall thermodynamic parameters do not depend on the detailed molecular mechanism for the reaction, whereas values of measured rate constants do reflect the mechanism. Recently,

The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexade-cyl... more The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexade-cylthiomethylbenzenes where X was a mesylate, chloride, or bromide was investigated using surface plasmon resonance (spr). The data were fit to a model in which nonspecific adsorption competes with a second-order substitution reaction between myoglobin and the surface species. The second-order reaction rate constants obtained from the regression analysis were 440 (140 M-1 s-1 for the bromide, 56 (10 M-1 s-1 for the mesylate, and 38 (12 M-1 s-1 for the chloride. The experimental rate law fit to the data and the increase in rate with decreased basicity of the leaving group were consistent with an SN2 mechanism.

Myoglobin is shown to bind to mixed thin films of docosyl mesylate and methyl docosanoate. Myoglo... more Myoglobin is shown to bind to mixed thin films of docosyl mesylate and methyl docosanoate. Myoglobin can be attached to films containing docosyl mesylate; however, films containing only methyl docosanoate exhibit only minimal myoglobin attachment. This indicates that myoglobin is specifically attached to the docosyl mesylate sites on the film surface. Surface coverage of myoglobin is dependent on the percentage of docosyl mesylate in the film. A maximum myoglobin coverage of approximately 1.2 × 10 12 myoglobin/cm 2 is estimated for films composed of between 22% and 30% docosyl mesylate.

Journal of The Optical Society of America B-optical Physics, 1986

The Journal of Physical Chemistry B, 2013

Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-pa... more Evidence for unexpected off-path intermediates to DNA duplex formation is presented. These off-path intermediates are shown to involve unimolecular and, in one case, bimolecular structure in one of the single strands of complementary DNA. Three models are developed to account for the observed single-stranded structures that are formed in parallel with duplex formation. These models are applied to the analysis of stopped-flow data for eight different nonself-complementary duplex formation reactions in order to extract the elementary rate constant for formation of the duplex from the complementary random coil single-stranded DNA. The free energy of activation (at 25 °C) for the denaturation of each duplex is calculated from these data and is shown to have a linear correlation to the overall standard free energy for duplex formation (also at 25 °C). Duplexes that contain mismatches obey a parallel linear free-energy (LFE) relationship with a y-intercept that is greater than that of duplexes without mismatches. Slopes near unity for the LFE relationships indicate that all duplexes go through an early, unstructured transition state.

The Journal of Physical Chemistry B, 2004

Langmuir, 1999

Synthesis of Docosyl Mesylate. The docosyl mesylate was prepared from 1-docosanol and excess meth... more Synthesis of Docosyl Mesylate. The docosyl mesylate was prepared from 1-docosanol and excess methyl sulfonyl chloride. A 5 g mass of 1-docosanol was placed in a 250 mL three-necked flask fitted with a dropping funnel, a drying tube, and a condenser. Approximately 50 mL of ...

Surface Science Letters

Reaction and desorption are competing surface processes and their product yields are dependent up... more Reaction and desorption are competing surface processes and their product yields are dependent upon both the surface heating rate and the kinetic parameters for reaction and desorption. Laser induced thermal desorption (LITD) is a useful probe of surface reactions because the desorption yield can often dominate the reaction yield at rapid laser induced heating rates. In this Letter, the relationship between the product yields for desorption and reaction as a function of surface heating rate was investigated numerically because an analytical equation does not exist. An empirical equation was determined that presents the functional relationship between the surface heating rate at which the product yields for reaction and desorption are 1 : 1 and the kinetic parameters for reaction and desorption. This equation is useful for predicting the experimental heating rates required for LITD studies of surface reaction kinetics.

Langmuir, 1994

... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and... more ... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and Terry Encalarde Department of Chemistry, College of the Holy Cross, Worcester, Massachusettes 01610 ... (26) Fischetti, RF; Filipkowski, M.; Gerito, A. F.; Blasie, JK Phys. ...

Langmuir, 1994

... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and... more ... Alice A. Deckert,' Lara Fallon,+ Lisa Kiernan,t Christopher Cashin, Anthony Perrone, and Terry Encalarde Department of Chemistry, College of the Holy Cross, Worcester, Massachusettes 01610 ... (26) Fischetti, RF; Filipkowski, M.; Gerito, A. F.; Blasie, JK Phys. ...

Langmuir, 1995

The first study of the polymerization and thermochromism in Langmuir-Blodgett films of the Cd2+ s... more The first study of the polymerization and thermochromism in Langmuir-Blodgett films of the Cd2+ salts of 5,7-docosadiynoic acid (DCDA) and 5,7-tretracosadiynoic acid (TTCDA) formed at molecular areas of 22 and 26 A2/molecule is reported. The polymerization behavior and ...

The Journal of Chemical Physics, 1988

ABSTRACT

The Journal of Chemical Physics, 1987

The decomposition reaction of methanol on Ru(001) was studied using laser induced thermal desorpt... more The decomposition reaction of methanol on Ru(001) was studied using laser induced thermal desorption (LITD). The LITD studies, combined with temperature programmed desorption and Auger electron spectroscopy measurements, allowed absolute product yields for the three competing surface pathways to be determined over the entire range of chemisorbed methanol coverages at a heating rate of β=2.6 K/s. At the lowest methanol coverages of θ≤0.07θs, where θs is the surface coverage of a saturated chemisorbed layer, all the methanol reacted between 220–280 K. This methanol decomposition reaction yielded desorption-limited H2 and CO as reaction products. At higher coverages, molecular desorption and the second methanol decomposition reaction involving C–O bond breakage became increasingly important. At θ=θs, 50% of the initial methanol coverage desorbed, 24% produced H2 and CO and 26% left C on the surface. Isothermal LITD kinetic measurements were carried out at low methanol coverages of θ≤0.07θs at various temperatures from 180 to 220 K. The initial decomposition rates obtained from the isothermal LITD studies displayed first order kinetics. The decomposition kinetics at later times could not be fit by first order kinetics and suggested a self-poisoned reaction. Subsequent LITD studies revealed that CO inhibited the decomposition reaction. The product CO inhibition was modeled by first order kinetics with a CO-coverage dependent activation barrier. The observed first order reaction kinetics at low methanol coverage could be expressed by the pre-exponential ν=106 s−1 and the coverage-dependent activation barrier E=7 kcal/mol+αθCO/θCO,s, where α=20 kcal/mol and θCO/θCO,s is the dimensionless CO coverage normalized to the CO saturation coverage θCO,s. Isotopic LITD studies revealed that the decomposition kinetics of CH3OH, CD3OH, and CH3OD were identical. This equivalence suggested that the hindered rotation of the surface methoxy species is the reaction coordinate for the rate-limiting step in the decomposition reaction.

The Journal of Chemical Physics, 1986

ABSTRACT

Journal of Chemical Education, 1998

... Physical Chemistry Laboratory Course Alice A. Deckert* and Lisa P. Nestor Department of Chemi... more ... Physical Chemistry Laboratory Course Alice A. Deckert* and Lisa P. Nestor Department of Chemistry, College of Holy Cross, Worcester, MA 01610 Donna DiLullo Department of Biology and Chemistry, Springfield College, Springrfield, MA 01109-3797 ... 22. Bodner, CM J. Chem. ...

Langmuir, 2002

The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexadecylt... more The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexadecylthiomethylbenzenes where X was a mesylate, chloride, or bromide was investigated using surface plasmon resonance (spr). The data were fit to a model in which nonspecific adsorption competes with a ...

Biochemistry, 2013

The rates of duplex formation for two octamers of DNA (5&... more The rates of duplex formation for two octamers of DNA (5' d-CACGGCTC/5' d-GAGCCGTG and 5' d-CACAGCAC/5' d-GTGCTGTG), the homologous RNA, and both sets of hybrids in 1 M NaCl buffer have been measured using stopped-flow spectroscopy. In addition, the thermodynamic parameters, ΔH° and ΔS°, have been determined for the same sequences under the same buffer conditions using optical melting techniques. These data reveal a linear free energy relationship between the free energy of activation for denaturation and the change in free energy for formation of the duplexes. This relationship indicates that these duplex formation reactions occur through a common unstructured transition state that is more similar to the single strands in solution than to the ensuing duplex. In addition, these data confirm that the greater stability of RNA duplexes relative to that of homologous DNA and hybrid duplexes is controlled by the denaturation rate and not the duplex formation rate.

The rates of duplex formation for two octamers of DNA (5′ d-CACGGCTC/5′ d-GAGCCGTG and 5′ d-CACAG... more The rates of duplex formation for two octamers of DNA (5′ d-CACGGCTC/5′ d-GAGCCGTG and 5′ d-CACAGCAC/5′ d-GTGCTGTG), the homologous RNA, and both sets of hybrids in 1 M NaCl buffer have been measured using stopped-flow spectroscopy. In addition, the thermodynamic parameters, ΔH° and ΔS°, have been determined for the same sequences under the same buffer conditions using optical melting techniques. These data reveal a linear free energy relationship between the free energy of activation for denaturation and the change in free energy for formation of the duplexes. This relationship indicates that these duplex formation reactions occur through a common unstructured transition state that is more similar to the single strands in solution than to the ensuing duplex. In addition, these data confirm that the greater stability of RNA duplexes relative to that of homologous DNA and hybrid duplexes is controlled by the denaturation rate and not the duplex formation rate. D uplex formation of nucleic acids is one of the most fundamental biological processes. RNA primers form a duplex with the parental strand DNA during replication. 1 Codon versus anticodon recognition requires the formation of a short stretch of duplex during translation. 2 SiRNAs, miRNAs, and piwiRNAs all form duplexes with their target sequences. 3−5 In addition, laboratory techniques such as polymerase chain reaction rely on duplex formation to complete a round of amplification. Therefore, understanding the molecular details of duplex formation will greatly facilitate our understanding of many processes central to the biology of the cell. The stability of nucleic acid duplexes has been investigated by multiple laboratories. 6−11 These results have led to the development of the nearest-neighbor model for predicting the stability of nucleic acid duplexes that takes into account the strength of H-bonding and base-stacking interactions. While there is some sequence specificity, in general RNA duplexes have been found to be more stable than either the DNA or DNA−RNA hybrid duplexes with similar sequences. 6−8 These models can generally predict the stability of duplexes to within approximately 0.5 kcal/mol or within a 2-fold range of the binding constant, but the underlying reason for the relative stability of the RNA duplexes is not well understood. A full understanding of the relative stability of homologous RNA and DNA duplexes can be obtained only by measuring both the equilibrium and kinetic parameters for the duplex formation equilibria under the same solvent conditions. Several early studies of the kinetics of duplex formation have led investigators to speculate that the stability of nucleic acid duplexes is controlled by the denaturation, or " off " , rate because the measured duplex formation, or " on " , rate constants tend to be similar regardless of sequence. 12 However, this speculation has not yet been rigorously tested. The base-by-base mechanism first proposed by Wetmur and Davidson 13 is the typical starting point for the interpretation of kinetic data. This mechanism has often been characterized in terms of a nucleation step followed by a fast zipping of the remaining base pairs. The first, rate-determining nucleation step takes single-stranded DNA or RNA to a nucleated duplex with two to four 14−16 H-bonded and stacked bases. Although most sources agree that only a few H-bonded bases exist in the nucleated intermediate, the number of base pairs that must align at the transition state has been estimated by Manning and others to be much higher, 15 or 16 bases. 17−19 This nucleation step is followed by a rapid zipping step in which the rest of the duplex base stacks and hydrogen bonds. Each of these steps most likely consists of individual base-by-base steps that cannot be distinguished and are thus treated as an ensemble or kinetic cluster. 20 In the steady state limit of this model, the nucleated intermediate is not kinetically significant, and this model correlates with the two-state model generally used to obtain thermodynamic parameters from melting data. In this limit, the on and off rate constants can be assigned to the formation and denaturation, respectively, of the nucleation site, which is rate-limiting. In contrast to the large thermodynamic data set for nucleic acid duplex formation found in the literature, the kinetic data set is much smaller. Whereas most thermodynamic studies have been conducted using the same solvent system (1 M NaCl), the existing kinetic data have been obtained under a variety of solvent conditions, making the correlation of these kinetic data with thermodynamic data difficult. Furthermore, the values of overall thermodynamic parameters do not depend on the detailed molecular mechanism for the reaction, whereas values of measured rate constants do reflect the mechanism. Recently,

The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexade-cyl... more The rate of the reaction between solution-phase myoglobin and SAMs fabricated from ω-X-hexade-cylthiomethylbenzenes where X was a mesylate, chloride, or bromide was investigated using surface plasmon resonance (spr). The data were fit to a model in which nonspecific adsorption competes with a second-order substitution reaction between myoglobin and the surface species. The second-order reaction rate constants obtained from the regression analysis were 440 (140 M-1 s-1 for the bromide, 56 (10 M-1 s-1 for the mesylate, and 38 (12 M-1 s-1 for the chloride. The experimental rate law fit to the data and the increase in rate with decreased basicity of the leaving group were consistent with an SN2 mechanism.

Myoglobin is shown to bind to mixed thin films of docosyl mesylate and methyl docosanoate. Myoglo... more Myoglobin is shown to bind to mixed thin films of docosyl mesylate and methyl docosanoate. Myoglobin can be attached to films containing docosyl mesylate; however, films containing only methyl docosanoate exhibit only minimal myoglobin attachment. This indicates that myoglobin is specifically attached to the docosyl mesylate sites on the film surface. Surface coverage of myoglobin is dependent on the percentage of docosyl mesylate in the film. A maximum myoglobin coverage of approximately 1.2 × 10 12 myoglobin/cm 2 is estimated for films composed of between 22% and 30% docosyl mesylate.