Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces

Magill, Brenden A.; Guo, Xi; Peck, Cheryl L.; Reyes, Roberto L.; See, Erich M.; Santos, Webster L.; Robinson, Hans D.

doi:10.1039/c8pp00346g

Cited by 6 publications

(7 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This means that for hot carriers to either tunnel into or be excited within the 1a-containing SAM, the ligands need to be lying down on the surface at least part of the time, so that the amine groups overlap with the electronic wave function of the metal, which extends about 10 Å from the surface. This is consistent with observations we have made on this SAM in a different context, 71 which indicate that SAMs made from 1 are of intermediate density, allowing the end group of 1 to spend at least part of the time in close proximity to the surface.…”

Section: Discussionsupporting

confidence: 92%

Plasmon-Induced Photoreaction of o-Nitrobenzyl-Based Ligands under 550 nm Light

et al. 2017

Self Cite

View full text Add to dashboard Cite

We have studied the plasmon-driven photoreaction of a dual thiol-anchored o-nitrobenzyl-based photouncaging ligand on silver nanoparticles. Previous results have shown that this compound strongly anchors to gold surfaces, and a 1 J/cm 2 dose of UV light induces the intended photoreaction, uncaging an amine on the surface. This allows for photopatterning and the selective adhesion of gold nanospheres (AuNSs) to a surface via electrostatic attraction between the positively charged amines and negatively charged AuNSs. Here, we report that when the ligand is adsorbed on a silver nanospheroid film (AgNS), an additional photoreaction induced by green light inhibits AuNSs adhesion in the UV exposed film. Our findings suggest that this is a result of the neutralization of the amine group's ability to become charged, as opposed to the removal of the ligand from the surface of the silver nanospheroids. We hypothesize that this neutralization may be due to a form of hot-hole-induced photocatalysis, resulting in an NN double bond between two neighboring ligands. This reaction has been documented in similarly amine-terminated moieties. This neutralization allows for a more fine-tuned, plasmonically based control of the ligand's photoreaction, as the green light exposure only affects the ligand if it has previously been cleaved by UV light, and makes it possible to perform reverse photopatterning on the surface.

show abstract

Section: Discussionsupporting

confidence: 92%

Plasmon-Induced Photoreaction of o-Nitrobenzyl-Based Ligands under 550 nm Light

et al. 2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…202 In the rest state, self-hybridized hairpins (42) and (43) were inert, since the trigger stand (41) was inactivated by photocaging of four thymine base constituents with ONB moieties, which prevented the strand from forming duplex hybrids. Irradiation of the system with UV light triggered the photocleavage of the protecting groups, activating the strand toward hybridization with the toehold of hairpin (42), triggering the HCR to generate polymeric duplexes, which was observed by gel electrophoretic separation from the monomeric precursors, Figure 9B. When hairpins (37) and (38) were exposed to the caged-(41) strand, the system remained dormant in the absence of UV light (Lane 1).…”

Section: Hairpin Chain Reactions and Fuel/catalyst Driven Cyclesmentioning

confidence: 99%

“…Moreover, the photoresponsive ortho-nitrobenzyl unit has been applied to develop a variety of technologies, including caged lightresponsive ion carriers such as Ca 2+ and Mg 2+ ionophores 33 and cryptands, 34 photoresponsive polymer networks 35 and photoresponsive hydrogels, 36,37 photoactivated prodrugs and drug delivery systems, 38 photocaged bioconjugates, 39 such as insulin, 40 for controlled release, aggregation of nanoparticles, 41 and surface patterning. 42 The advances in using the orthonitrobenzyl protective group in chemical synthesis and diverse applications were summarized in several comprehensive review articles. 35,37,38,43,44 The base sequence comprising oligonucleotide biopolymers encodes substantial functional and structural information into these biopolymers.…”

Section: Introductionmentioning

confidence: 99%

Photocleavable Ortho-Nitrobenzyl-Protected DNA Architectures and Their Applications

et al. 2023

View full text Add to dashboard Cite

This review article introduces mechanistic aspects and applications of photochemically deprotected ortho-nitrobenzyl (ONB)-functionalized nucleic acids and their impact on diverse research fields including DNA nanotechnology and materials chemistry, biological chemistry, and systems chemistry. Specific topics addressed include the synthesis of the ONB-modified nucleic acids, the mechanisms involved in the photochemical deprotection of the ONB units, and the photophysical and chemical means to tune the irradiation wavelength required for the photodeprotection process. Principles to activate ONB-caged nanostructures, ONB-protected DNAzymes and aptamer frameworks are introduced. Specifically, the use of ONB-protected nucleic acids for the phototriggered spatiotemporal amplified sensing and imaging of intracellular mRNAs at the single-cell level are addressed, and control over transcription machineries, protein translation and spatiotemporal silencing of gene expression by ONB-deprotected nucleic acids are demonstrated. In addition, photodeprotection of ONB-modified nucleic acids finds important applications in controlling material properties and functions. These are introduced by the phototriggered fusion of ONB nucleic acid functionalized liposomes as models for cell–cell fusion, the light-stimulated fusion of ONB nucleic acid functionalized drug-loaded liposomes with cells for therapeutic applications, and the photolithographic patterning of ONB nucleic acid-modified interfaces. Particularly, the photolithographic control of the stiffness of membrane-like interfaces for the guided patterned growth of cells is realized. Moreover, ONB-functionalized microcapsules act as light-responsive carriers for the controlled release of drugs, and ONB-modified DNA origami frameworks act as mechanical devices or stimuli-responsive containments for the operation of DNA machineries such as the CRISPR-Cas9 system. The future challenges and potential applications of photoprotected DNA structures are discussed.

show abstract

“…Previous reports on o NB monolayers have focused on spatially resolved techniques at fixed time points, including optical spectroscopy and secondary fluorescence staining; [ 67,68 ] chemical characterization with grazing‐angle infrared spectroscopy and x‐ray‐photoelectron spectroscopy, [ 69–71 ] or physical characterization via atomic force microscopy and contact angle measurements. [ 71,72 ] To fully understand what is occurring at the interface during light irradiation, time resolved techniques that can quantitatively measure chemical changes at the interface are critical. Quartz crystal microbalance with dissipation monitoring (QCM‐D) was investigated in this project as a technique that could provide real time quantitation of the photochemical reaction occurring on the surface, not possible with other routine techniques (see discussion above).…”

Section: Resultsmentioning

confidence: 99%

“…Previous reports on oNB mono layers have focused on spatially resolved techniques at fixed time points, including optical spectroscopy and secondary fluorescence staining; [67,68] chemical characterization with grazing-angle infrared spectroscopy and x-ray-photoelectron spectroscopy, [69][70][71] or physical characterization via atomic force microscopy and contact angle measurements. [71,72] To fully understand what is occurring at the interface during light irradiation, time resolved techniques that can quantitatively measure chemical changes at First, the grafting of light-sensitive nitroxide linkers 11 and 12 to the surface, was investigated to determine grafting kinetics and grafting density. The formation of silane films in toluene at 40 °C was extremely rapid, as seen by both the frequency and dissipation curves in QCM-D (Figure 5a).…”

Section: Grafting Of Light Sensitive Surfacesmentioning

confidence: 99%

A Versatile Light‐Triggered Radical‐Releasing Surface Coating Technology

Boase

Michalek

Hooker

et al. 2021

Adv Materials Technologies

View full text Add to dashboard Cite

Organic based redox active materials and coatings are increasingly being investigated as solutions for more efficient energy devices, catalysts, sensors, and biomedical technologies. Their advantage is negating the necessity for expensive and unsustainable rare earth metals seen in other redox active materials. Challenges to their wide‐spread usage remain, including versatility of coatings on a wide range of substrates, and creating smart devices that can respond to environmental stimuli. A new light responsive radical releasing redox coating has been developed, that can be rapidly and stably applied to a diverse range of substrates including silicon dioxide, plastics, and microparticles. These coatings rapidly cleave upon irradiation with UV‐A light to release stable nitroxides from the surface coating. These coatings are developed into microparticle sensors for radical oxygen species, which are able to detect the generation of free radicals in a model system for particulate matter pollution. These new responsive organic redox coatings also offer future potential to function as switchable organic electrodes, and biomedical surface coatings to prevent biofouling and reduce inflammation.

show abstract

Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces

Abstract: We demonstrate photocleavage of gold-bound ligands by two-photon absorption usable for light-directed nanoassembly and high resolution optical lithography.

Cited by 6 publications

References 67 publications

Plasmon-Induced Photoreaction of o-Nitrobenzyl-Based Ligands under 550 nm Light

Plasmon-Induced Photoreaction of o-Nitrobenzyl-Based Ligands under 550 nm Light

Photocleavable Ortho-Nitrobenzyl-Protected DNA Architectures and Their Applications

A Versatile Light‐Triggered Radical‐Releasing Surface Coating Technology

Contact Info

Product

Resources

About