Sampling the Self-Assembly Pathways of KFFE Hexamers

Abstract The template effect is a key feature to control the arrangement of building blocks in assemblies, but its kinetic nature remains elusive compared to the thermodynamic aspects, with the exception of very simple reactions. Here we report a kinetic template effect in a self-assembled cage composed of flexible ditopic ligands and Pd(II) ions. Without template anion, a micrometer-sized sheet is kinetically trapped (off-pathway), which is converted into the thermodynamically most stable cage by the template anion. When the template anion is present from the start, the cage is selectively produced by the preferential cyclization of a dinuclear intermediate (on-pathway). Quantitative and numerical analyses of the self-assembly of the cage on the on-pathway revealed that the accelerating effect of the template is stronger for the early stage reactions of the self-assembly than for the final cage formation step itself, indicating the kinetic template effect.

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Revealing the Self-Assembly Pathways and Nanomechanics of Enzyme-Triggered Nanofibers from Peptide Amphiphiles for Cancer Theranostics

Biophysical Journal ◽

10.1016/j.bpj.2015.11.949 ◽

2016 ◽

Vol 110 (3) ◽

pp. 170a

Author(s):

Hsien-Shun Liao ◽

Peng Huang ◽

Yuan Gao ◽

Edward Cai ◽

Ferenc Horkay ◽

...

Keyword(s):

Self Assembly ◽

The Self ◽

Peptide Amphiphiles ◽

Cancer Theranostics ◽

Assembly Pathways

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Controlling the self-assembly pathways of amphiphilic block copolymers into vesicles

Soft Matter ◽

10.1039/c2sm25281c ◽

2012 ◽

Vol 8 (30) ◽

pp. 7865 ◽

Cited By ~ 44

Author(s):

Mengying Xiao ◽

Guangjie Xia ◽

Rong Wang ◽

Daiqian Xie

Keyword(s):

Block Copolymers ◽

Self Assembly ◽

The Self ◽

Amphiphilic Block Copolymers ◽

Assembly Pathways

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Hydrophobic domain flexibility enables morphology control of amphiphilic systems in aqueous media

Chemical Communications ◽

10.1039/d0cc06173e ◽

2020 ◽

Vol 56 (89) ◽

pp. 13808-13811

Author(s):

Ingo Helmers ◽

Nils Bäumer ◽

Gustavo Fernández

Keyword(s):

Self Assembly ◽

Aqueous Media ◽

Morphology Control ◽

The Self ◽

Hydrophobic Domain ◽

Aggregate Morphology ◽

The Impact ◽

Assembly Pathways

In this work, we unravel the impact of hydrophobic domain flexibility on the self-assembly pathways and aggregate morphology of amphiphilic systems in aqueous media.

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Evaluation of Self-Assembly Pathways to Control Crystallization-Driven Self-Assembly of a Semicrystalline P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) Triblock Copolymer

Molecules ◽

10.3390/molecules25174033 ◽

2020 ◽

Vol 25 (17) ◽

pp. 4033

Author(s):

Enrique Folgado ◽

Matthias Mayor ◽

Vincent Ladmiral ◽

Mona Semsarilar

Keyword(s):

Self Assembly ◽

Triblock Copolymer ◽

Vinylidene Fluoride ◽

The Self ◽

Selective Solvents ◽

Poly Vinylidene Fluoride ◽

Self Assembled ◽

Assembly Behavior ◽

Assembly Pathways ◽

Induced Crystallization

To date, amphiphilic block copolymers (BCPs) containing poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) copolymers are rare. At moderate content of HFP, this fluorocopolymer remains semicrystalline and is able to crystallize. Amphiphilic BCPs, containing a P(VDF-co-HFP) segment could, thus be appealing for the preparation of self-assembled block copolymer morphologies through crystallization-driven self-assembly (CDSA) in selective solvents. Here the synthesis, characterization by 1H and 19F NMR spectroscopies, GPC, TGA, DSC, and XRD; and the self-assembly behavior of a P(VDF-co-HFP)-b-PEG-b-P(VDF-co-HFP) triblock copolymer were studied. The well-defined ABA amphiphilic fluorinated triblock copolymer was self-assembled into nano-objects by varying a series of key parameters such as the solvent and the non -solvent, the self-assembly protocols, and the temperature. A large range of morphologies such as spherical, square, rectangular, fiber-like, and platelet structures with sizes ranging from a few nanometers to micrometers was obtained depending on the self-assembly protocols and solvents systems used. The temperature-induced crystallization-driven self-assembly (TI-CDSA) protocol allowed some control over the shape and size of some of the morphologies.

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Self-assembly pathways and polymorphism in peptide-based nanostructures

Nanoscale ◽

10.1039/c7nr06724k ◽

2018 ◽

Vol 10 (3) ◽

pp. 1508-1516 ◽

Cited By ~ 15

Author(s):

Nikola A. Dudukovic ◽

Benjamin C. Hudson ◽

Anant K. Paravastu ◽

Charles F. Zukoski

Keyword(s):

Self Assembly ◽

The Self ◽

Solute Interactions ◽

Assembly Pathways

The effects of solvent–solute interactions on the self-assembly of a dipeptide molecule into nanofibers are explored.

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Measurements of the self-assembly kinetics of individual viral capsids around their RNA genome

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.1909223116 ◽

2019 ◽

Vol 116 (45) ◽

pp. 22485-22490 ◽

Cited By ~ 12

Author(s):

Rees F. Garmann ◽

Aaron M. Goldfain ◽

Vinothan N. Manoharan

Keyword(s):

Self Assembly ◽

Failure Modes ◽

The Self ◽

Coat Proteins ◽

Viral Capsids ◽

Functional Nanostructures ◽

Assembly Kinetics ◽

Collective Phenomenon ◽

Assembly Pathways ◽

Kinetics Of

Self-assembly is widely used by biological systems to build functional nanostructures, such as the protein capsids of RNA viruses. But because assembly is a collective phenomenon involving many weakly interacting subunits and a broad range of timescales, measurements of the assembly pathways have been elusive. We use interferometric scattering microscopy to measure the assembly kinetics of individual MS2 bacteriophage capsids around MS2 RNA. By recording how many coat proteins bind to each of many individual RNA strands, we find that assembly proceeds by nucleation followed by monotonic growth. Our measurements reveal the assembly pathways in quantitative detail and also show their failure modes. We use these results to critically examine models of the assembly process.

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Solution Self-Assembly of Coil-Crystalline Diblock Copolypeptoids Bearing Alkyl Side Chains

Polymers ◽

10.3390/polym13183131 ◽

2021 ◽

Vol 13 (18) ◽

pp. 3131

Author(s):

Naisheng Jiang ◽

Donghui Zhang

Keyword(s):

Self Assembly ◽

Building Blocks ◽

The Self ◽

Side Chains ◽

Two Dimensional ◽

Biotechnological Applications ◽

One Dimensional ◽

Alkyl Side Chains ◽

Assembly Behavior ◽

Assembly Pathways

Polypeptoids, a class of synthetic peptidomimetic polymers, have attracted increasing attention due to their potential for biotechnological applications, such as drug/gene delivery, sensing and molecular recognition. Recent investigations on the solution self-assembly of amphiphilic block copolypeptoids highlighted their capability to form a variety of nanostructures with tailorable morphologies and functionalities. Here, we review our recent findings on the solutions self-assembly of coil-crystalline diblock copolypeptoids bearing alkyl side chains. We highlight the solution self-assembly pathways of these polypeptoid block copolymers and show how molecular packing and crystallization of these building blocks affect the self-assembly behavior, resulting in one-dimensional (1D), two-dimensional (2D) and multidimensional hierarchical polymeric nanostructures in solution.

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Understanding the self-assembly pathways of a single chain variant of monellin: A first step towards the design of sweet nanomaterials

International Journal of Biological Macromolecules ◽

10.1016/j.ijbiomac.2020.02.229 ◽

2020 ◽

Vol 152 ◽

pp. 21-29

Author(s):

Masoud Delfi ◽

Serena Leone ◽

Alessandro Emendato ◽

Diletta Ami ◽

Margherita Borriello ◽

...

Keyword(s):

Self Assembly ◽

The Self ◽

Single Chain ◽

Assembly Pathways ◽

Chain Variant

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The Nature of Rapidly Extracted Phycocyanin from the Blue-Green Alga Plectonema Boryanum

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100065870 ◽

1971 ◽

Vol 29 ◽

pp. 366-367

Author(s):

M. Kessel ◽

R. MacColl

Keyword(s):

Self Assembly ◽

Analytical Ultracentrifugation ◽

Uranyl Acetate ◽

The Self ◽

Major Protein ◽

Subunit Structure ◽

Blue Green Alga ◽

Thin Sections ◽

Blue Green Algae ◽

Cacodylate Buffer

The major protein of the blue-green algae is the biliprotein, C-phycocyanin (Amax = 620 nm), which is presumed to exist in the cell in the form of distinct aggregates called phycobilisomes. The self-assembly of C-phycocyanin from monomer to hexamer has been extensively studied, but the proposed next step in the assembly of a phycobilisome, the formation of 19s subunits, is completely unknown. We have used electron microscopy and analytical ultracentrifugation in combination with a method for rapid and gentle extraction of phycocyanin to study its subunit structure and assembly.To establish the existence of phycobilisomes, cells of P. boryanum in the log phase of growth, growing at a light intensity of 200 foot candles, were fixed in 2% glutaraldehyde in 0.1M cacodylate buffer, pH 7.0, for 3 hours at 4°C. The cells were post-fixed in 1% OsO4 in the same buffer overnight. Material was stained for 1 hour in uranyl acetate (1%), dehydrated and embedded in araldite and examined in thin sections.

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