Solid-Phase Incorporation of an ATRP Initiator for Polymer-DNA Biohybrids (original) (raw)
Related papers
ACS Macro Letters, 2019
An aqueous electrochemically mediated atom transfer radical polymerization (eATRP) was performed in a small volume solution (75 μL) deposited on a screen-printed electrode (SPE). The reaction was open to air, thanks to the use of glucose oxidase (GOx) as an oxygen scavenger. Welldefined poly(2-(methylsulfinyl)ethyl acrylate) (PMSEA), poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA), and corresponding DNA−polymer biohybrids were synthesized by the small-volume eATRP at room temperature. The reactions were simplified and polymerization rates increased by the application of the enzyme deoxygenating system and the compact electrochemical setup. Importantly, the volume of polymerization mixture was lowered to microliters, which not only decreases the cost for each reaction, but can also be potentially implemented in combinatorial chemistry and electrode-array configurations for high-throughput systems.
Dynamic and Responsive DNA-like Polymers
Journals of the American Chemical Society, 2018
The synthesis of thiolactone monomers that mimic natural nucleosides and engage in robust ring opening polymerizations (ROP) is herein described. As each repeat unit contains a thioester functional group, dynamic rearrangement of the polymer is feasible via thiol-thioester exchange, demonstrated here by depolymerization of the polymers and coalescing of two polymers of different molecular weight or chemical composition. This approach constitutes the first step toward a platform that enables for the routine synthesis of sequence controlled polymers via dynamic template directed synthesis.
Development of albumin macroinitiator for polymers to use in DNA origami coating
TURKISH JOURNAL OF MEDICAL SCIENCES, 2020
Background/aim: DNA nanostructures have many advantages over polymers and lipid based drug delivery agents such as biodegradability and biocompatibility. However their transfection rates and stability still limit their widely use in nanomedicine. In this study highly versatile and straightforward albumin coating preparation method is showed for DNA nanostructures. Materials and methods: N-methylolmaleimide was esterified with a-bromoisobutyrl bromide (BiBB) to achive bromine functional structure. Then it was attached to bovine serum albumin (BSA) via cysteine-maleimide bond further to use as macroinitiator for atom transfer radical polymerization (ATRP). Cationic polymers can be synthesized from this end further to use as binding domain for fabricated 60 Helix bundle DNA origami. Results: Proton nuclear magnetic resonance (1 H NMR) analysis used for characterization. Methyelene group hydrogens' peak in 5.0 ppm and strong peak in 1.5-2.0 ppm range showed proper methylolation of maleimide and bromine functional formation, respectively. Then BSA-macroinitiator formation is verified by 1780 Da peak shift in MALDI-TOF (Matrix-assisted laser desorption/ionizationtime of flight) spectrum. Moreover electrophoretic mobility shift assay (EMSA) showed successful dense 60 Helix bundle formation. Conclusion: In this study, a facile method is developed to synthesize protein conjugated-ATRP initiator further can be used in polymerization and coating DNA nanostructures. It is feasible for any protein containing cysteine amino acid.
Signal-Amplifying Conjugated Polymer–DNA Hybrid Chips
Angewandte Chemie, 2007
Bio-/synthetic hybrid materials have recently received considerable attention owing to their potential biomedical applications. [1] The most reliable way of identifying any biological target is through its genetic code. However, the current commercial DNA microarray requires costly and time-consuming PCR to multiply the number of analyte DNA molecules and label the analyte DNA with a fluorescent dye because of the low detection limit. In this context, devising self-signal-amplifying DNA microarrays can realize low-cost, fast, and reliable detection of nucleic acids. Herein, we report signal-amplifying DNA chips fabricated by on-chip DNA synthesis on a thin film of a newly developed conjugated polymer ( and the chemical structure in Figure 2 a).
Constructing novel materials with DNA
Nano Today, 2007
Although the detailed structure of DNA was revealed by Watson and Crick 1,2 back in 1953, even today we continue to discover stunning and useful new structural modes for this versatile macromolecule. Taking lessons from its in vivo role and aided by technological advances, nanoengineers have begun to explore novel and creative uses for DNA including: molecular detection 3 , therapeutic regimens 4 , complex nanodevices 5 , nanomechanical actuators and motors 6-8 , directed organic synthesis 9,10 , and molecular computation 11,12 . Excellent reviews of many of these aspects of DNA can be found in this issue of Nano Today and elsewhere 10,12,13 .
Biomaterials, 2005
A series of comb-type copolymers comprised of various polycation backbones and dextran (Dex) side chains were prepared to study the DNA/copolymer interaction. While the cationic copolymers with a lower degree of dextran grafts maintained an ability to condense DNA molecules into a globule form those with a higher degree of dextran grafting interacted with DNA without inducing DNA condensation. The structural differences in cationic backbones diversely influenced DNA hybridization as evaluated by circular dichroism (CD) spectrometry and UV-melting analyses. The copolymer having a polyallylamine (PAA) backbone induced B-A-type transformation of DNA duplex, whereas the copolymers having either a-poly(l-lysine) (aPLL) or e-poly(l-lysine) (ePLL) backbone induced B-C-type transformation. The PAA copolymer is the first example of the artificial polymer that induces B-A-type transformation under physiologically relevant condition. UV-melting analyses of DNA strands indicated that the aPLL copolymers showed the highest stabilization efficacy toward poly(dA) Á poly(dT) duplex and poly(dA) Á 2poly(dT) triplex without affecting reversibility of inter DNA association. Melting temperatures (T m ) of the triplex increased from 38 C to 99 C by the addition of the aPLL copolymer with an appropriate grafting degree. While the PAA copolymers had higher density of cationic groups along the backbone than aPLL copolymers, these copolymers moderately increased T m of the DNA triplex. The PAA copolymer caused considerable hysteresis in thermal melting/reassociation processes. Note that the ePLL copolymers increased T m of the DNA triplex and not the duplex, suggesting their potential as a triplex selective stabilizer. Chemical structures of the cationic backbones of the copolymers were characteristically affected on the copolymer/DNA interaction even if their backbones were surrounded by abundant side chains (> 65 wt%) of dextran. The study suggested that tailor-made design of ''functional polycounterion'' is a strategy to engineer molecular assembling of DNA. r