Preparation of Spherical Nucleic Acid Nanoparticles Containing a Self-immolative Poly(carbamate) Core

Fukumoto, Shione; Kawade, Mami; Kimura, Kazunori; Akiyama, Yoshitsugu; Kikuchi, Akihiko

doi:10.2116/analsci.20scn06

Cited by 3 publications

(3 citation statements)

References 17 publications

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“…Self-immolative polymers (SIPs) are a class of degradable polymers that undergo end-to-end depolymerization to small molecules after the cleavage of their backbone or stabilizing end-cap by a stimulus. − Unlike traditional degradable or stimuli-responsive polymers, only a single bond cleavage is needed to initiate complete SIP degradation. This property makes SIPs attractive for applications such as sensing, , patterning, − degradable/recyclable plastics, − and drug delivery, − where an amplified or highly sensitive response to stimuli is desired. Several SIP backbones have been developed, including poly(benzyl carbamates), , poly(benzyl ethers), poly(acetals), − poly(olefin sulfones), , and more recently poly(benzyl esters), polythioesters, , polycarboxypyrroles, polycyclopentenes, and polydisulfides .…”

Section: Introductionmentioning

confidence: 99%

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

et al. 2021

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Self-immolative polymers (SIPs) are characterized by their ability to depolymerize in response to the cleavage of a single end-cap or backbone moiety, making them attractive for numerous applications including sensors, transient plastics, and delivery vehicles. For many applications, it would be desirable to have an SIP capable of depolymerizing selectively under mildly acidic aqueous conditions. However, the poor solubility of most SIPs in water, accompanied by the competing effects of end-cap cleavage and depolymerization mechanisms, has made this a challenge. Here, we describe the development of polyglyoxylamides (PGAms) with pendent amino groups to achieve solubility switching at mildly acidic pH, which allows access of water to the end-cap and consequently depolymerization. PGAms with varying amino groups were synthesized from trityl end-capped poly(ethyl glyoxylate) (PEtG). While water-insoluble PEtG underwent no detectable depolymerization between pH 5 and 7.4 and water-soluble PGAms underwent rapid depolymerization regardless of pH in this range, a PGAm with N,N-diisopropylaminoethyl (DPAE) pendent groups underwent more rapid depolymerization at pH 5−6 compared to pH 7.4. PGAms were also incorporated into block copolymers with poly(ethylene glycol) (PEG). Nanoassemblies formed from PEG-PGAm(DPAE), swelled, disassembled, and depolymerized as the pH was lowered from 8 to 5. Copolymers lacking a solubility switch did not undergo pH-dependent disassembly or depolymerization. Overall, this work provides a new platform approach for the development of pH-sensitive SIP materials for a wide range of applications.

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Section: Introductionmentioning

confidence: 99%

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

et al. 2021

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“…The majority of examples associated with self-immolative polymers are based on polybenzylcatbamates, most likely due to the simplicity of the monomer budling blocks and the efficiency of the polymerization protocol. Therefore, numerous publications describing various applications with such self-immolative polymers have appeared during the past few years. − In addition to the examples described so far in this Perspective, several other polymer backbones with related disassembly mechanism have recently been reported. − Moreover, the progress of the field has inspired scientists to develop polymers that employ a self-immolative dendritic unit as a focal junction for disassembly. Such polymers usually carry a responsive group on their self-immolative dendritic unit, which is attached to two polymeric side chains.…”

Section: Miscellaneous Examples Of Polymers With Related Self-immolat...mentioning

confidence: 99%

Self-Immolative Polymers: An Emerging Class of Degradable Materials with Distinct Disassembly Profiles

2021

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Self-immolative polymers are an emerging class of macromolecules with distinct disassembly profiles that set them apart from other general degradable materials. These polymers are programmed to disassemble spontaneously from head to tail, through a domino-like fragmentation, upon response to extremal stimuli. In the time since we first reported this unique type of molecule, several groups around the world have developed new, creative molecular structures that perform analogously to our pioneering polymers. Self-immolative polymers are now widely recognized as an important class of stimuli-responsive materials for a wide range of applications such as signal amplification, biosensing, drug delivery, and materials science. The quinone-methide elimination was shown to be an effective tool to achieve rapid domino-like fragmentation of polymeric molecules. Thus, numerous applications of self-immolative polymers are based on this disassembly chemistry. Although several other fragmentation reactions achieved the function requested for sequential disassembly, we predominantly focused in this Perspective on examples of self-immolative polymers that disassemble through the quinone-methide elimination. Selected examples of self-immolative polymers that disassembled through other chemistries are briefly described. The growing demand for stimuli-responsive degradable materials with novel molecular backbones and enhanced properties guarantees the future interest of the scientific community in this unique class of polymers.

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“…However, only a limited number of investigations have been focused on the preparation of SNA with dense layer of nucleic acids attached to the polymer core surface. SNA with the self-immolative poly(carbamate) core covered with a dense DNA shell have been reported by Fukumoto et al [29]. Polyesters such as poly(ε-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) have been used to prepare SNAs as well.…”

Section: Introductionmentioning

confidence: 99%

Nanoarchitectonics of Spherical Nucleic Acids with Biodegradable Polymer Cores: Synthesis and Evaluation

et al. 2022

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Spherical nucleic acids (SNAs) have gained significant attention due to their unique properties allowing them to overcome the challenges that face current nanocarriers used for gene therapies. The aim of this study is to synthesize and characterize polymer–oligonucleotide conjugates of different architecture and to evaluate the possibility of forming SNAs with biodegradable cores. Initially, two types of azide (multi)functional polyester-based (co)polymers were successfully synthesized and characterized. In the next step, short oligonucleotide strands were attached to the polymer chains applying the highly efficient and metal-free “click” reaction, thus forming conjugates with block or graft architecture. Both conjugates spontaneously self-assembled in aqueous media forming nanosized SNAs with a biodegradable polyester core and a surface of oligonucleotide chains as evidenced from dynamic and electrophoretic light scattering measurements. The nano-assemblies were in vitro evaluated for potential cytotoxicity. Furthermore, the interactions of the newly synthesized SNAs with membrane lipids were studied. The preliminary results indicate that both types of polymer-based SNAs are good candidates for potential application in gene therapy and that it is worth to be further evaluated.

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Preparation of Spherical Nucleic Acid Nanoparticles Containing a Self-immolative Poly(carbamate) Core

Cited by 3 publications

References 17 publications

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

Polyglyoxylamides with a pH-Mediated Solubility and Depolymerization Switch

Self-Immolative Polymers: An Emerging Class of Degradable Materials with Distinct Disassembly Profiles

Nanoarchitectonics of Spherical Nucleic Acids with Biodegradable Polymer Cores: Synthesis and Evaluation

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