Thermosetting supramolecular polymerization of compartmentalized DNA fibers with stereo sequence and length control

Dore, Michael D.; Trinh, Tuan; Zorman, Marlo L.; Rochambeau, Donatien de; Platnich, Casey M.; Xu, Pengfei; Luo, Xin; Remington, Jacob M.; Toader, Violeta; Cosa, Gonzalo; Li, Jianing; Sleiman, Hanadi F.

doi:10.1016/j.chempr.2021.05.022

Cited by 20 publications

(22 citation statements)

References 62 publications

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“…This amphiphile undergoes thermallydriven supramolecular polymerisation to form long, one-dimensional fibers (Figures 1a and 2c): 9 the hydrophobic block curls at elevated temperatures to expose the phosphates and hide the C12 chains, promoting fusion and fiber elongation (Figure 1a). 9 By increasing the length of the hydrophilic DNA segment, we expect the self-assembly morphology to change following principles of microphase separation: as the amphiphilic packing parameter decreases, we expect assemblies with increasing interfacial curvature. 15 Tuning the relative length of polymer blocks is an efficient tool for controlling morphology: a size-and shape-defined DNA nanostructure may be assembled from a single molecular species, and each different morphology can influence cellular uptake and bioactivity properties.…”

Section: Changing Dna Lengthmentioning

confidence: 96%

“…Upon cooling, our C1212-A19 fibers aggregate into hierarchical superstructures (Figure 5), whereas C1212-DNA19 is observed as individual long fibers by AFM. 9 The assembly of C1212-A19 into superstructures occurs upon cooling in the range 60-50 °C, as shown by hypochromicity in the UVvis spectra (Figure 5e). The rate of cooling was observed to significantly affect the resulting morphology: Single fibers, two or three fibers in parallel, and starburst fiber structures resulted from rapid cooling (50 °C min -1 ), whereas slow cooling at 0.2 °C min -1 resulted in large, interwoven, and threaded architectures, as observed by AFM (Figure 5c).…”

Section: Changing Dna Sequencementioning

confidence: 99%

“…Sequence-defined DNA amphiphiles are covalent polymer chains of monodisperse length and specific monomer order attached to single-stranded DNA, constructed efficiently and rapidly on an automated DNA synthesizer. [1][2][3][4][5][6][7][8][9][10] Self-assembly arises to minimize contact of the hydrophobic region with water, and the relative volume of the hydrophobic to hydrophilic block can play a major role in determining the assembly morphology. [11][12][13] Increasing the volume of the hydrophobic phase generally decreases the interfacial curvature (i.e., the curvature of the hydrophobic region at the interface between the two blocks) evolving the morphology from spheres to cylinders to lamellae.…”

Section: Introductionmentioning

confidence: 99%

“…14,15 In the case of DNA block copolymers, this yields supramolecular structures with DNA coronas that can be addressed with functional moieties for numerous biological and materials applications. 7,[16][17][18][19][20] Our group 3,9,[21][22][23] and others 24,25 have explored modulation of the hydrophobic moiety -its size, chemistry and number of repeat monomers -in forming diverse structures, but rarely has altering the hydrophilic DNA chain been investigated as a driving force in self-assembly. 26,27 Single-stranded DNA (ssDNA) chains are not always disordered polymers -electrostatics, π interactions, and base hydrophobicity can alter the conformation, rigidity, and internal structure of ssDNA.…”

Section: Introductionmentioning

confidence: 99%

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DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

Rizzuto

Dore

Rafique

et al. 2022

Preprint

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The self-assembly of block copolymers is often rationalized by structure and microphase separation; pathways that diverge from this parameter space may provide new mechanisms of polymer self-assembly. Here, we show that the sequence and length of single-stranded DNA directly influence the self-assembly of sequence-defined DNA block copolymers. While increasing the length of DNA led to predictable changes in self-assembly, changing only the sequence of DNA produced three distinct structures: spherical micelles (spherical nucleic acids, SNAs) from flexible poly(thymine) DNA, fibers from semi-rigid mixed-sequence DNA, and networked superstructures from rigid poly(adenine) DNA. The secondary structure of poly(adenine) DNA strands drives a temperature-dependent polymerization and assembly mechanism: copolymers stored in an SNA reservoir form fibers after thermal activation, which then aggregate upon cooling to form interwoven networks. DNA is often used as a programming code that aids in nanostructure addressability and function; Here, we show that the inherent physical and chemical properties of single-stranded DNA sequences also make them an ideal material to direct self-assembled morphologies and select for new methods of supramolecular polymerization.

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Section: Changing Dna Lengthmentioning

confidence: 96%

Section: Changing Dna Sequencementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

Rizzuto

Dore

Rafique

et al. 2022

Preprint

View full text Add to dashboard Cite

show abstract

“…Sequence-defined DNA amphiphiles are covalent polymer chains of monodisperse length and specific monomer order attached to single-stranded DNA, constructed efficiently and rapidly on an automated DNA synthesizer. − Self-assembly arises to minimize contact of the hydrophobic region with water, and the relative volume of the hydrophobic to hydrophilic block can play a major role in determining the assembly morphology. − Increasing the volume of the hydrophobic phase generally decreases the interfacial curvature (i.e., the curvature of the hydrophobic region at the interface between the two blocks) evolving the morphology from spheres to cylinders to lamellae. , In the case of DNA block copolymerswhere DNA is the hydrophilic segment, attached covalently to a block of hydrophobic monomersthis yields supramolecular structures with DNA coronas that can be addressed with functional moieties for numerous biological and materials applications. ,− …”

Section: Introductionmentioning

confidence: 99%

DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

et al. 2022

Self Cite

View full text Add to dashboard Cite

The self-assembly of block copolymers is often rationalized by structure and microphase separation; pathways that diverge from this parameter space may provide new mechanisms of polymer assembly. Here, we show that the sequence and length of single-stranded DNA directly influence the self-assembly of sequence-defined DNA block copolymers. While increasing the length of DNA led to predictable changes in selfassembly, changing only the sequence of DNA produced three distinct structures: spherical micelles (spherical nucleic acids, SNAs) from flexible poly(thymine) DNA, fibers from semirigid mixed-sequence DNA, and networked superstructures from rigid poly(adenine) DNA. The secondary structure of poly(adenine) DNA strands drives a temperature-dependent polymerization and assembly mechanism: copolymers stored in an SNA reservoir form fibers after thermal activation, which then aggregate upon cooling to form interwoven networks. DNA is often used as a programming code that aids in nanostructure addressability and function. Here, we show that the inherent physical and chemical properties of single-stranded DNA sequences also make them an ideal material to direct self-assembled morphologies and select for new methods of supramolecular polymerization.

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Precision Sequence‐Defined Polymers: From Sequencing to Biological Functions

Shi,

Zhang,

Liu

2023

Angewandte Chemie

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Precise sequence‐defined polymers (SDPs) with uniform chain‐to‐chain structure including chain length, unit sequence and end functionalities, represent the pinnacle of sophistication in the realm of polymer science. For example, the absolute control over the unit sequence of SDPs allows for bottom‐up design of polymers with hierarchical microstructures and functions. Accompanied with the development of synthetic techniques towards precision SDPs, the decoding of SDP sequences and construction of advanced functions irreplaceable with other synthetic materials is of central importance. In this Minireview, we focus on recent advances in SDP sequencing techniques including tandem mass spectrometry (MS), chemically assisted primary MS, as well as other non‐destructive sequencing methods such as nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), and nanopore sequencing. Additionally, we delve into the promising prospects of SDP functions in the area of cutting‐edge biological research. Topics of exploration include gene delivery systems, the development of hybrid materials combining SDPs and nucleic acids, protein recognition and regulation, as well as the interplay between chirality and biological functions. A brief outlook towards the future directions of SDPs is also presented.

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Thermosetting supramolecular polymerization of compartmentalized DNA fibers with stereo sequence and length control

Cited by 20 publications

References 62 publications

DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

DNA Sequence and Length Dictate the Assembly of Nucleic Acid Block Copolymers

Precision Sequence‐Defined Polymers: From Sequencing to Biological Functions

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