Light-emitting self-assembled peptide nucleic acids exhibit both stacking interactions and Watson–Crick base pairing (original) (raw)
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Nature Communications
The variety and complexity of DNA-based structures make them attractive candidates for nanotechnology, yet insufficient stability and mechanical rigidity, compared to polyamide-based molecules, limit their application. Here, we combine the advantages of polyamide materials and the structural patterns inspired by nucleic-acids to generate a mechanically rigid fluorenylmethyloxycarbonyl (Fmoc)-guanine peptide nucleic acid (PNA) conjugate with diverse morphology and photoluminescent properties. The assembly possesses a unique atomic structure, with each guanine head of one molecule hydrogen bonded to the Fmoc carbonyl tail of another molecule, generating a non-planar cyclic quartet arrangement. This structure exhibits an average stiffness of 69.6 ± 6.8 N m−1 and Young’s modulus of 17.8 ± 2.5 GPa, higher than any previously reported nucleic acid derived structure. This data suggests that the unique cation-free “basket” formed by the Fmoc-G-PNA conjugate can serve as an attractive compon...
Self-Assembling of Fmoc-GC Peptide Nucleic Acid Dimers into Highly Fluorescent Aggregates
Chemistry - A European Journal
Self-assembling of molecules by non-covalent interactions is one of the most attracting topics in supramolecular chemistry. The use of short peptides or modified nucleotides as building blocks of the aggregates is particularly intriguing, as these are very easy to synthesize; moreover subtle changes in the chemical structure of such building blocks may drastically affect the properties of the aggregates. The ability of Peptide Nucleic Acids to aggregate is yet very little explored, despite its practical applications. In this work we investigated the self-assembling properties of a PNA dimer, conjugated at the N-terminus to a fluorenylmethoxycarbonyl group. This PNA dimer forms nano-aggregates at low concentration in CHCl 3 /CH 3 OH mixtures. The aggregates keep very interesting fluorescent properties (high quantum yield in the visible region with lifetime in the nanoseconds scale), which make them a promising material for applications in optoelectronic.
Nucleic acid-based nanoengineering: novel structures for biomedical applications
Interface Focus, 2011
Nanoengineering exploits the interactions of materials at the nanometre scale to create functional nanostructures. It relies on the precise organization of nanomaterials to achieve unique functionality. There are no interactions more elegant than those governing nucleic acids via Watson-Crick base-pairing rules. The infinite combinations of DNA/RNA base pairs and their remarkable molecular recognition capability can give rise to interesting nanostructures that are only limited by our imagination. Over the past years, creative assembly of nucleic acids has fashioned a plethora of two-dimensional and three-dimensional nanostructures with precisely controlled size, shape and spatial functionalization. These nanostructures have been precisely patterned with molecules, proteins and gold nanoparticles for the observation of chemical reactions at the single molecule level, activation of enzymatic cascade and novel modality of photonic detection, respectively. Recently, they have also been engineered to encapsulate and release bioactive agents in a stimulus-responsive manner for therapeutic applications. The future of nucleic acid-based nanoengineering is bright and exciting. In this review, we will discuss the strategies to control the assembly of nucleic acids and highlight the recent efforts to build functional nucleic acid nanodevices for nanomedicine.
Chemistry – A European Journal, 2019
Studies carried out in the last decades have unveiled that the ability to self-assemble is a widespread property among biomolecules. Small nucleic acid moieties or very short peptides are able to generate intricate assemblies endowed with remarkable structural and spectroscopic properties. Here we report structural/spectroscopic characterizations of aggregates formed by nucleobases as well as by Peptide Nucleic Acids (PNA)-peptide conjugates. At high concentration, all studied nucleobases form aggregates characterized by previously unreported fluorescence properties. The conjugation of these bases, as PNA derivatives, to the dipeptide Phe-Phe leads to the formation of novel hybrid assemblies, characterized by an amyloid-like association of the monomers. Although these compounds share the same basic cross-β motif, the nature and the number of PNA units have an important impact both on the level of structural order and on the intrinsic fluorescence of the self-assembled nanostructure.
Self-Assembly of Diphenylalanine–Peptide Nucleic Acid Conjugates
ACS Omega, 2019
The synthesis and self-assembled nanostructures of a series of nucleopeptides (NPs) derived from the dipeptide Phe−Phe and the peptide nucleic acid unit which are covalently attached through an amide or a triazole linker are described. Depending on the variables such as protecting groups, linkers, and nucleobases, spherical nanoparticles were observed through scanning electron microscopy and high-resolution transmission electron microscopy images, and the porous nature of representative NPs was corroborated by carboxyfluorescein entrapment. Hydrophobic substituents on different sites of NPs and solvents employed for peptide self-assembly played a crucial role for corresponding morphologies. The stability of nanoparticles was also probed under external stimuli such as pH, temperature, and enzymatic hydrolysis using proteolytic enzymes. The semiconducting nature of the NP-modified carbon electrodes suggested their potential use as a new capacitor material.
Toward electronically-functional, self-assembling DNA nanostructures
Journal of self-assembly and molecular electronics, 2018
Recent work has demonstrated that DNA, ordinarily considered a weak conductor, can be functionalized to carry electronic charge by site-specific incorporation of single silver ions inside the double helix via the non-canonical pairing of mismatched cytosines through Ag + coordination: (dC:Ag + :dC) [1,2]. Through the alteration of sequence composition and cation availability, a variety of nanowires can be synthesized with tuneable length, ion distribution, and uniformity. These wires are more thermostable than Watson-Crick DNA, can shield intercalated Ag + from aqueous solvents, and are able to form in the absence of cluster contamination. We use computational sequence design algorithms to introduce nonlinear geometry to these nanowires, with the goal of creating self-assembling DNA nanostructures that may have potential for neural architectures from electrically-functional oligonucleotide components.
Short self-assembling peptides as building blocks for modern nanodevices
2012
Short, self-assembling peptides form a variety of stable nanostructures used for the rational design of functional devices. Peptides serve as organic templates for conjugating biorecognition elements, and assembling ordered nanoparticle arrays and hybrid supramolecular structures. We are witnessing the emergence of a new phase of bionanotechnology, particularly towards electronic, photonic and plasmonic applications. Recent advances include self-assembly of photoluminescent semiconducting nanowires and peptide-conjugated systems for sensing, catalysis and energy storage. Concurrently, methods and tools have been developed to control and manipulate the self-assembled nanostructures. Furthermore, there is growing knowledge on nanostructure properties such as piezoelectricity, dipolar electric field and stability. This review focuses on the emerging role of short, linear self-assembling peptides as simple and versatile building blocks for nanodevices.
Ordered Self-Assembled Monolayers of Peptide Nucleic Acids with DNA Recognition Capability
Physical Review Letters, 2004
We report on the formation of ordered self-assembled monolayers (SAMs) of single-stranded peptide nucleic acids (ssPNA). In spite of their remarkable length (7 nm) thiolated PNAs assemble standing up on gold surfaces similarly to the SAMs of short alkanethiols. SAMs of ssPNA recognize complementary nucleic acids, acting as specific biosensors that discriminate even a point mutation in target ssDNA. These results are obtained by surface characterization techniques that avoid labeling of the target molecule: x-ray photoemission, x-ray absorption and atomic force microscopy.
Organic & Biomolecular Chemistry, 2008
The influence of added polynucleotide on the gelation ability of nucleobase-appended organogelators was investigated. Uracil-appended cholesterol gelator formed a stable organogel in polar organic solvents such as n-butanol. It was found that the addition of the complementary polyadenylic acid (poly(A)) not only stabilizes the gel but also creates the helical structure in the original gel phase. Thymidine and thymine-appended gelators can form stable gel in apolar solvents, such as benzene, where poly(A)-lipid complex can act as a complementary template for the gelator molecules to create the fibrous composites. Based on these findings, we can conclude that self-assembling modes and gelation properties of nucleobase-appended organogelators are controllable by the addition of their complementary polynucleotide in organic solvents. We believe, therefore, that the present system can open the new paths to accelerate development of well-controlled one-dimensional molecular assembly systems, which would be indispensable for the creation of novel nanomaterials based on organic compounds.