Microcontact insertion printing

Mullen, Tracy; Srinivasan, Charan; Hohman, J. Nathan; Gillmor, Susan D.; Shuster, Mitchell J.; Horn, Mark W.; Andrews, Anne M.; Weiss, Paul S.

doi:10.1063/1.2457525

Cited by 51 publications

(95 citation statements)

References 24 publications

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“…37,38 After exposing the alkanethiolate SAMs to guest molecules either in solution, vapor, or by contact (e.g., with a patterned polymer stamp), single molecules can be selectively inserted at the defect sites. 3,23,26,27,30,31,[39][40][41][42][43][44][45] Due to physical constraints from the surrounding matrix and (optional) designed intermolecular interactions, the inserted molecules are limited in their motion and stabilized in specific conformations. The resulting surface structure, as shown in Figure 1c, consists of isolated molecules protruding from host SAM matrices, enabling measurements of driven molecular switching at the single-molecule level by STM.…”

Section: Self-assembly and Measurementsmentioning

confidence: 99%

Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles

Li¹,

Paxton²,

Baughman³

et al. 2009

MRS Bull.

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Recent developments in chemical synthesis, nanoscale assembly, and molecularscale measurements enable the extension of the concept of macroscopic machines to the molecular and supramolecular levels. Molecular machines are capable of performing mechanical movements in response to external stimuli. They offer the potential to couple electrical or other forms of energy to mechanical action at the nano-and molecular scales. Working hierarchically and in concert, they can form actuators referred to as artificial muscles, in analogy to biological systems. We describe the principles behind driven motion and assembly at the molecular scale and recent advances in the field of molecular-level electromechanical machines, molecular motors, and artificial muscles. We discuss the challenges and successes in making these assemblies work cooperatively to function at larger scales.

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Section: Self-assembly and Measurementsmentioning

confidence: 99%

Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles

Li¹,

Paxton²,

Baughman³

et al. 2009

MRS Bull.

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“…Such surfaces and functionalization chemistries are being optimized for other neurotransmitters, such as dopamine and norepinephrine. These derivatized monolayers also can be patterned into separate areas of single substrates using soft or hybrid lithographies [28,29] so as to enable multiplexed capture of biomolecule binding partners specific for individual brain neurotransmitter systems. In summary, we have designed and assembled surfaces functionalized with the small molecule serotonin that are accessible for recognition by large biomolecule binding partners.…”

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confidence: 99%

Biospecific Recognition of Tethered Small Molecules Diluted in Self‐Assembled Monolayers

et al. 2007

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A model system for the capture of large biomolecule targets by small-molecule probes has been developed using a combination of insertion self-assembly and chemical functionalization. Key to selective molecular recognition of small molecules is the ability to tether these such that they are readily accessible for binding. This is particularly challenging because the tether alters a significant fraction of the probe molecule. It is also critical to space small-molecule probes so that they are dilute and exposed, rather than clustered via phase separation on capture surfaces, particularly when trying to bind large-molecule targets (e.g., proteins, nucleic acids). [1][2][3][4][5] Optimal dilution avoids the effects of steric hindrance [6][7][8] and multivalent non-specific interactions. Dilute surface coverage is also important to enable strategies to prevent nonspecific binding. We have developed a general method for addressing these problems [5,[9][10][11][12] and apply these to surfaces functionalized with the small-molecule neurotransmitter serotonin (5-hydroxytryptamine; Fig. 1). Serotonin is covalently bound to tethers inserted at dilute coverage into pre-existing self-assembled monolayers (SAMs) bearing a molecular surface of oligo(ethylene glycol). We chose serotonin as our initial probe both because of its important roles as a neurotransmitter involved in anxiety and mood disorders [13] and as a prototypical small molecule for which many high-affinity binding proteins have been identified [14] but for which many more remain unknown. We demonstrate access to and specific recognition of serotonin by comparing the capture from solution of antibodies directed against serotonin versus those specific for another neurotransmitter, dopamine, or the enzyme tyrosine hydroxylase. We also show that these surfaces resist nonspecific protein adsorption of bovine serum albumin (BSA). Previous attempts by us using analogous preparations on alkylamine-functionalized sepharose beads failed because they were fraught with nonspecific binding. The assembly/synthetic strategy described produces a smallmolecule-derivatized surface capable of biospecific recognition. This approach is readily translatable to most neurotransmitters, as well as to many other small molecules. In addition to identifying selective molecular recognition elements for future biosensor applications, these serotonin-functionalized surfaces will be used in combination with mass spectrometry to identify and to characterize expression patterns of brain proteins, such as membrane-associated receptors, that selectively bind to serotonin in experiments designed to investigate the etiologies of psychiatric disorders and their treatments. [15][16][17] Serotonin-derivatized surfaces were prepared using a fourstep process. Monolayers of oligo(ethylene-glycol)-terminated alkanethiol (1) were self-assembled on Au substrates. These SAMs have been prepared previously [7,8,[18][19][20][21][22] and resist nonspecific binding of proteins (extra care is taken to minimize film ...

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“…It is important to note that in the overlapping patterned regions, the tether molecules (which are functionalized with smallmolecule probes) are isolated such that they do not interact with other probe molecules in the surrounding region. This molecular isolation can be controlled and influenced by many factors and has been confirmed by both ensemble and localized analytical techniques (Mullen et al 2007a;Shuster et al 2008).…”

Section: Chemically Patterned Surfacesmentioning

confidence: 99%

“…In contrast, the molecular composition of chemically patterned films created by microcontact insertion printing (lCIP) is controlled by other factors such as the density of defects in the initial substrate, the stamping duration, and the concentration of the patterned molecules. Microcontact insertion printing enables dilute and isolated molecules to be patterned within a background SAM matrix, in a way that is not possible by other lithographic strategies (Mullen et al 2007a;Srinivasan et al 2007). Diffusion of the inserted molecules is also prevented, as in lDP.…”

Section: Chemically Patterned Surfacesmentioning

confidence: 99%

“…A key advantage of LACP, lCIP, and related techniques is the ability to fabricate chemical films of isolated single molecules or bundles of molecules diluted within a background matrix over large areas. The molecular composition of the chemical pattern is influenced by the extent of insertion of the patterned molecules, which can be controlled by tuning the patterning duration, the concentration of the patterned molecules, the quality of the preexisting SAM, and the intermolecular interaction strengths of both the preexisting SAM and the patterned or inserted molecules (Mullen et al 2007a). This control of molecular composition and isolation is particularly critical for small-molecule functionalized surfaces.…”

Section: Chemically Patterned Surfacesmentioning

confidence: 99%

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Hybrid approaches to nanometer-scale patterning: Exploiting tailored intermolecular interactions

et al. 2008

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In this perspective, we explore hybrid approaches to nanometer-scale patterning, where the precision of molecular self-assembly is combined with the sophistication and fidelity of lithography. Two areas--improving existing lithographic techniques through self-assembly and fabricating chemically patterned surfaces--will be discussed in terms of their advantages, limitations, applications, and future outlook. The creation of such chemical patterns enables new capabilities, including the assembly of biospecific surfaces to be recognized by, and to capture analytes from, complex mixtures. Finally, we speculate on the potential impact and upcoming challenges of these hybrid strategies.

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Microcontact insertion printing

Cited by 51 publications

References 24 publications

Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles

Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles

Biospecific Recognition of Tethered Small Molecules Diluted in Self‐Assembled Monolayers

Hybrid approaches to nanometer-scale patterning: Exploiting tailored intermolecular interactions

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