A novel class of compounds, known as peptide nucleic acids, bind complementary ssDNA and RNA strands more strongly than a corresponding DNA. The peptide nucleic acids generally comprise ligands such as naturally occurring DNA bases attached to a peptide backbone through a suitable linker.

/pdf/peptide-nucleic-acids-1hpyrn4znw.pdf

Peptide nucleic acids

2.1.6. Tacticity and Sequence: Advanced Control 4967 2.2. Transition Metal Catalysts 4967 2.2.1. Overviews of Catalysts 4967 2.2.2. Ruthenium 4967 2.2.3. Copper 4971 2.2.4. Iron 4971 2.2.5. Nickel 4975 2.2.6. Molybdenum 4975 2.2.7. Manganese 4976 2.2.8. Osmium 4976 2.2.9. Cobalt 4976 2.2.10. Other Metals 4976 2.3. Cocatalysts (Additives) 4977 2.3.1. Overview of Cocatalysts 4977 2.3.2. Reducing Agents 4977 2.3.3. Free Radical Initiators 4977 2.3.4. Metal Alkoxides 4977 2.3.5. Amines 4978 2.3.6. Halogen Source 4978 2.4. Initiators 4978 2.4.1. Overview of Initiators: Scope and Design 4978 2.4.2. Alkyl Halides 4978 2.4.3. Arenesulfonyl Halides 4979 2.4.4. N-Chloro Compounds 4979 2.4.5. Halogen-Free Initiators 4979 2.5. Solvents 4980 2.5.1. Overview of Solvents 4980 2.5.2. Catalyst Solubility and Coordination of Solvent 4981 2.5.3. Environmentally Friendly Solvents 4981 2.5.4. Water 4981 2.5.5. Catalytic Solvents: Catalyst Disproportionation 4981

Transition metal-catalyzed living radical polymerization : toward perfection in catalysis and precision polymer synthesis

Background During the last few decades, progress has been made in manipulating the architecture of synthetic polymer materials. However, the primary structure—that is, the sequential arrangement of monomer units in a polymer chain—is generally poorly controlled in synthetic macromolecules. Common synthetic polymers are usually homopolymers, made of the same monomer unit, or copolymers with simple chain microstructures, such as random or block copolymers. These polymers are used in many areas but do not have the structural and functional complexity of sequence-defined biopolymers, such as nucleic acids or proteins. Indeed, monomer sequence regulation plays a key role in biology and is a prerequisite for crucial features of life, such as heredity, self-replication, complex self-assembly, and molecular recognition. In this context, developing synthetic polymers containing controlled monomer sequences is an important area for research. Precise molecular encoding of synthetic polymer chains. In most synthetic copolymers, monomer units (represented here as colored square boxes A, B, C, and D) are distributed randomly along the polymer chains (left). In sequence-controlled polymers, they are arranged in a speciﬁc order in all of the chains (right). Monomer sequence regularity strongly inﬂuences the molecular, supramolecular, andmacroscopic properties of polymer materials. Advances Various synthetic methods for controlling monomer sequences in polymers have been identified, and two major trends in the field of sequence-controlled polymers have emerged. Some approaches use biological concepts that have been optimized by nature for sequence regulation. For instance, DNA templates, enzymes, or even living organisms can be used to prepare sequence-defined polymers. These natural mechanisms can be adapted to tolerate nonnatural monomers. The other trend is the preparation of sequence-controlled polymers by synthetic chemistry. In the most popular approach, monomer units are attached one by one to a support, which is an efficient method but demanding in practice. Recently, some strategies have been proposed for controlling sequences in chain-growth and step-growth polymerizations. These mechanisms usually allow fast and large-scale synthesis of polymers. Specific kinetics and particular catalytic or template conditions allow sequence regulation in these processes. Outlook The possibility of controlling monomer sequences in synthetic macromolecules has many scientific and technological implications. Information can be controlled at the molecular level in synthetic polymer chains. This opens up interesting perspectives for the field of data storage. In addition, having power over monomer sequences could mean structural control of the resulting polymer, as it strongly influences macromolecular folding and self-assembly. For instance, functional synthetic assemblies that mimic the properties of globular proteins, such as enzymes and transporters, can be foreseen. Moreover, monomer sequence control influences some macroscopic properties. For example, bulk properties such as conductivity, rigidity, elasticity, or biodegradability can be finely tuned in sequence-controlled polymers. The behavior of polymers in solution, particularly in water, is also strongly dependent on monomer sequences. Thus, sequence regulation may enable a more effective control of structure-property relations in tomorrow’s polymer materials.

http://science.sciencemag.org/content/sci/341/6146/1238149.full.pdf

Sequence-controlled polymers.

A novel class of compounds, known as peptide nucleic acids, bind complementary DNA and RNA strands more strongly than a corresponding DNA strand, and exhibit increased sequence specificity and solubility. The peptide nucleic acids comprise ligands selected from a group consisting of naturally-occurring nucleobases and non-naturally-occurring nucleobases attached to a polyamide backbone, and contain C1-C8 alkylamine side chains. Methods of enhancing the solubility, binding affinity and sequence specificity of PNAs are provided.

https://orbit.dtu.dk/files/58073632/US5736336.pdf

Peptide nucleic acids having enhanced binding affinity, sequence specificity and solubility

A novel class of compounds, known as peptide nucleic acids, bind complementary DNA and RNA strands more strongly than the corresponding DNA or RNA strands, and exhibit increased sequence specificity and solubility. The peptide nucleic acids comprise ligands selected from a group consisting of naturally-occurring nucleobases and non-naturally-occurring nucleobases attached to a polyamide backbone, and contain alkylamine side chains.

Peptide nucleic acids having amino acid side chains

In order to prepare simply designed nucleic acid models with high functionality, a series of polymeric compounds containing purine and pyrimidine bases as pendant, functional side groups were prepared successfully from their corresponding monomers by either polymerization or polycondensation techniques. As for the functionality of the polymers prepared, specific base-base interactions were studied in detail by measuring UV, NMR and emission spectroscopies. The specific interaction study was particularly made on poly-L-Lysine derivatives having nucleic acid bases in relation to their molecular weight, their conformation in solutions and other properties. From photodimerization study on the model compounds containing thymine bases, intramolecular features of the reaction were elucidated. Owing to the specific properties of the polymers, the studies will find a number of application possibilities, including separation techniques and polymeric drug chemistry. Graft copolymers of nucleic acid bases on polyethyleneimine were also concerned.

Synthetic nucleic acid analogs preparation and interaction

Polymerization of methyl methacrylate and other vinyl monomers was studied in the presence of oligoamide (ϵ-aminocaproic acid, its dimer, trimer, tetramer, and pentamer) and cupric ion in aqueous media. The polymerization was found to be of free-radical character and selective for the type of vinyl monomer. Carbon tetrachloride can accelerate the polymerization. The initiation mechanism of the polymerization is discussed. Spectroscopic measurements were indicative of formation of 1:1 complex between oligoamides and cupric ion in aqueous NaClO4 solution. Some chemical and physical properties of the resulting polymers were measured.

Vinyl polymerization by metal complexes. III. Vinyl polymerization initiated by oligoamide and cupric ion system

Time-resolved infrared spectral measurements were made successfully for studying the microscopic mechanism of water-induced solid-state phase transitions of poly(ethylene imine) (PEI) in the hydrat

Structural Investigation on Water-Induced Phase Transitions of Poly(ethylene imine). 1. Time-Resolved Infrared Spectral Measurements in the Hydration Process

Synthetic nucleic acid analogs

Oligonucleotide-based DNA microarrays are becoming increasingly useful tools for the analysis of gene expression and single nucleotide polymorphisms (SNPs). Here, we present a method that permits the manufacture of microarrays from non-modified oligonucleotides on a poly carbodiimide-coated glass surface by UV-irradiation. The use of UV-irradiation facilitates an increase in the level of signal intensity, but it does not affect signal discrimination by the oligonucleotides immobilized on the surface. The signal intensity obtained for an array fabricated using non-modified oligonucleotides with UV-irradiation is approximately 7-fold greater than that without UV-irradiation. The detection of SNPs was tested to ascertain whether this technique could discriminate specific hybridization signals without causing significant UV-irradiation-induced damage to the immobilized oligonucleotides. We found that this immobilization method provides greater hybridization signals and a better match/mismatch ratio of SNPs than do the established aminosilane techniques. Application of this technology to manufacturing DNA microarrays for sequence analysis is discussed.

/pdf/attachment-of-oligonucleotide-probes-to-poly-carbodiimide-bnc1zw8dko.pdf

Yoshiaki Inaki

Papers

Synthetic nucleic acid analogs preparation and interaction

Vinyl polymerization by metal complexes. III. Vinyl polymerization initiated by oligoamide and cupric ion system

Structural Investigation on Water-Induced Phase Transitions of Poly(ethylene imine). 1. Time-Resolved Infrared Spectral Measurements in the Hydration Process

Synthetic nucleic acid analogs

Attachment of oligonucleotide probes to poly carbodiimide-coated glass for microarray applications