Wavelength-Selective Light-Responsive DASA-Functionalized Polymersome Nanoreactors

Rifaie‐Graham, Omar; Ulrich, S Schubert; Galensowske, Nikolas F. B.; Balog, Sandor; Chami, Mohamed; Rentsch, Daniel; Hemmer, James R.; Alaniz, Javier Read de; Boesel, Luciano F.; Bruns, Nico

doi:10.1021/jacs.8b04511

Cited by 159 publications

(202 citation statements)

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“…[1] Light, as ar eadily available and adjustable reactiont rigger,i sp articularly interesting for implementing spatiotemporal control on reaction outcomes. [18][19][20] The isomerization of DASAsi sd ependent on the prevailing conditions, such as solvent,t emperature, concentration, or pH. [2][3][4][5] Photoswitches, such as derivatives of the donor-acceptor Stenhouse adduct (DASA), coexisti na ne quilibrium between two isomeric forms.O ne isomer consists of an intensely colored (blue, purple or orange)n onpolar linear form, whereas the other isomer is cyclized, polar,c olorless and commonly zwitterionic (Scheme 1).…”

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confidence: 99%

“…The cyclization mechanism hasbeen clarified in ac areful study by Feringa and Buma,i nw hichd ensity functional theory calculationsa nd transient absorption kinetics measurements were employed. [18][19][20] The isomerization of DASAsi sd ependent on the prevailing conditions, such as solvent,t emperature, concentration, or pH. [10][11][12][13] Clarification of the cyclization mechanism resulted in ap ool of DASA photoswitches bearing avariety of acceptorand donor functionalitiesaswell as an improvedk nowledge of factors influencing the switching process.…”

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It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

Alves

Wiedbrauk

Gräfe

et al. 2020

Chemistry A European J

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Donor-acceptor Stenhousea dducts( DASA) are popularp hotoswitches capable of togglingb etween two isomersd epending on the light and temperature of the system.T he cyclized polar form is accessed by visible-light irradiation, whereas the linear nonpolar form is recovered in the dark. Upon the formation of the cyclized form,t he DASA contains ad ouble bond featuring a b-carbonp rone to nucleophilica ttack.H ere, an isomer selective thiol-Michael reaction betweenthe cyclized DASA and ab ase-activated thiol is introduced. The thiol-Michael addition was carried out with an alkyl (1-butanethiol) and an aromatic thiol (p-bromothiophenol) as reaction partners, both in the presence of ab ase. Undero ptimized conditions,t he reactionp roceeds preferentially in the presenceo fl ight and base. The current study demonstrates that DASAsc an be selectively trapped in their cyclized state.Molecular photoswitches undergo reversible isomerization upon irradiation with light, and sometimes in combination with ad ifferent stimulus, for example, temperature. [1] Light, as ar eadily available and adjustable reactiont rigger,i sp articularly interesting for implementing spatiotemporal control on reaction outcomes. For example, photoswitches are employed for biomedical andb iochemical processes including targetedd rug delivery and chemical/biological sensing applications. [2][3][4][5] Photoswitches, such as derivatives of the donor-acceptor Stenhouse adduct (DASA), coexisti na ne quilibrium between two isomeric forms.O ne isomer consists of an intensely colored (blue, purple or orange)n onpolar linear form, whereas the other isomer is cyclized, polar,c olorless and commonly zwitterionic (Scheme 1). [6][7][8][9] The equilibrium between the two forms is dependent on the solvente nvironment andt he structural motifs of the DASA derivatives, consistingo fa ne lectron donor and an acceptorm oiety,r esultingi napush-pull system.U pon irradiation, the equilibrium is shifted towardst he ring cyclized isomer (cyclized form) and, upon thermalr elaxation, it returns to the initialc onjugated state (linear form). The cyclization mechanism hasbeen clarified in ac areful study by Feringa and Buma,i nw hichd ensity functional theory calculationsa nd transient absorption kinetics measurements were employed. [32] The current consensus on the cyclization processi nvolves isomerizationo ft he double bonds, followedby ab ond rotation, and finallyathermal conrotatory4 p electrocyclization leading to the cyclized ring, commonly stabilizedb yi ts zwitterionic form through ap roton transfer. [10][11][12][13] Clarification of the cyclization mechanism resulted in ap ool of DASA photoswitches bearing avariety of acceptorand donor functionalitiesaswell as an improvedk nowledge of factors influencing the switching process. [8,9,14,15] The inherent advantages of DASA photoswitches, which includesn egative photochromism, inexpensives tarting materials, modular synthesis, tunable absorption, visible-light switching, and good fatiguer esistance, are appealing for ar ...

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confidence: 99%

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confidence: 99%

It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

Alves

Wiedbrauk

Gräfe

et al. 2020

Chemistry A European J

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“…Another interesting work regarding light‐responsive polymersome nanoreactors based on Donor‐Acceptor Stenhouse Adducts (DASAs) was recently reported by Bruns and co‐workers . The polymers consisted of hydrophilic PEG and hydrophobic poly(pentafluorophenyl methacrylate) (PFPMA) and poly(hexyl methacrylate) (HMA).…”

Section: Stimuli‐responsive Polymersome Nanoreactorsmentioning

confidence: 99%

“…Another interesting work regarding light-responsive polymersome nanoreactors based on Donor-Acceptor Stenhouse Adducts (DASAs) was recently reported by Bruns and coworkers. [33] The polymers consisted of hydrophilic PEG and hydrophobic poly(pentafluorophenyl methacrylate) (PFPMA) and poly(hexyl methacrylate) (HMA). The aromatic amine precursor N-(4-methoxyphenyl)-1,3-diaminepropane (MPDP) was conjugated to the randomly distributed activated ester segments over the hydrophobic block, yielding DASA-bearing block copolymers.…”

Section: Light-responsive Polymersome Nanoreactorsmentioning

confidence: 99%

Adaptive Polymersome Nanoreactors

Che

Hest

2019

ChemNanoMat

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Adaptive polymersome systems have gained much interest in a wide variety of research fields, ranging from cell mimics to nanomedicine, because of their high stability, tunable shape and size. Furthermore, polymersomes can be effectively transformed into nanoreactors via the incorporation of catalytic species. By employing polymersomes which are adaptive in structure and function the features of polymersome nanoreactors can be even further extended. In this review, we focus on recent impressive developments of smart polymersomes as functional nanoreactors with an emphasis on the type of adaptivity that is installed, which includes intrinsic permeability, stimuli‐responsiveness and self‐adaptivity. Moreover, particular attention is given to the utility of polymersome nanoreactors in vitro and in vivo, which paves the next step forward towards the engineering of artificial organelles as therapeutic materials.

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“…The developed nanocapsules could act as on/off states by excitation of visible light and vice versa through the isomerization ability of donor–acceptor stenhouse adducts (DASAs) attached on the capsule periphery. The isomerization upon visible light illumination led to the permeability change of the polymersome membrane that is potentially promising also for drug delivery applications . In principle, the idea behind the light response for the nanocapsules formed either by self‐assembly or covalent approaches is the same as adding the photoactive moieties to the polymer shell.…”

Section: Nanocapsules With Controlled Release Propertiesmentioning

confidence: 99%

Modular Approach for the Design of Smart Polymeric Nanocapsules

İyisan

Landfester

2018

Macromol. Rapid Commun.

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embracing layer-by-layer assembly (LBL) methods, [4][5][6] and iii) self-assembly of the amphiphilic block copolymers. [7][8][9] In principle, the formation of the polymer shell that covers the core space is triggered by either covalent or non-covalent bonding depending on the selected method. The heterophase polymerization systems consist of (mini)emulsions and suspensions resulting in the covalently linked polymers covering the core-forming droplets. On the other hand, the miniemulsion technology also provides the opportunity to make capsules from preformed polymers when the polymerization cannot be performed in heterophase systems as shown by Landfester et al. [10][11][12] Miniemulsion polymerization is understood as a polymerization technique where stable droplets are formed prior to polymerization and the droplets are then polymerized. LBL approaches are commonly used in combination with templating methods. The principle is to use an organic or inorganic particle as a support in which the polymers are either adsorbed or grown by surface initiated polymerization (SIP) techniques on the surface of the particle template. [13] In this approach, different types and sized particles made of gold, silica, and carbonate are utilized as platforms. The template particles are further removed through etching procedures such as dissolution in acids to produce hollow capsules having a polymer shell. [6] Another promising way of polymeric nanocapsule formation is to use the self-assembly of specially designed amphiphilic block copolymers in water which in turn leads to polymersomes comprising a bilayer membrane and an aqueous core. [7] These vesicular structures are artificial mimetics of the liposomes that are self-assembled from natural phospholipids. Polymersomes showed various outstanding properties over their lipid counterparts such as higher mechanical strength, enhanced stability as well as a wide range of chemical versatility that enhances application opportunities in nanomedicine. [14,15] Several excellent reviews about polymeric nanocapsules focusing on their synthesis through miniemulsion processes, [1][2][3]16,17] templating approaches including layer-by-layer assemblies [4][5][6]18] as well as self-assembly processes [8,14,[19][20][21][22][23] have been published. Generally, their use in biomedical science including drug delivery and synthetic biology is underlined. However, there are relatively few examples of comparative reviews [13,[24][25][26][27][28][29] to emphasize the application-oriented eligibilities of the polymeric nanocapsules formed by different methods. In this context, we aim to discuss from a modular perspective both self-assembled nanocapsules, so-called polymersomes, and nanocapsules with a covalently formed shell, mainly obtained by the miniemulsion technique (Figure 1). NanocapsulesThe formation of nanocapsules from a modular perspective for self-assembled nanocapsules, so-called polymersomes, and nanocapsules with a covalently formed shell are discussed in this review. It is shown that the...

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Wavelength-Selective Light-Responsive DASA-Functionalized Polymersome Nanoreactors

Cited by 159 publications

References 80 publications

It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

It's a Trap: Thiol‐Michael Chemistry on a DASA Photoswitch

Adaptive Polymersome Nanoreactors

Modular Approach for the Design of Smart Polymeric Nanocapsules

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