Chemistry / Kimya
Permanent URI for this collectionhttps://hdl.handle.net/11147/4072
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Article Citation - WoS: 20Citation - Scopus: 22A New Proton Sponge Polymer Synthesized by Raft Polymerization for Intracellular Delivery of Biotherapeutics(Royal Society of Chemistry, 2014) Kurtuluş, Işıl; Yılmaz, Gökhan; Üçüncü, Muhammed; Emrullahoğlu, Mustafa; Becer, C. Remzi; Bulmuş, VolgaA spermine-like polymer was synthesized via reversible addition- fragmentation chain transfer polymerization as a potential endosomal escaping agent. A new methacrylate monomer, 2-((tert-butoxycarbonyl)(2-((tert- butoxycarbonyl)amino)ethyl)amino)ethylmethacrylate (BocAEAEMA), was prepared and then polymerized via RAFT polymerization at constant monomer or initiator concentration at varying [M]/[R]/[I] ratios. In all polymerizations, ln[M] 0/[M] increased linearly with time. The linear increase in M n with monomer conversion was also observed. P(BocAEAEMA)s with controlled molecular weights and narrow molecular weight distributions were obtained. The in vitro cytotoxicity and proton sponge capacity of deprotected polymers P(AEAEMA) were investigated in comparison with a widely used endosomal-disruptive polymer, PEI. P(AEAEMA)s were found to possess proton sponge capacity comparable with PEI. More importantly, P(AEAEMA)s were not toxic on NIH 3T3 cells at concentrations where PEI (25 kDa) was highly toxic (0.4 μM and above). P(AEAEMA) was able to fully condense a DNA fragment at nitrogen/phosphate (N/P) ratios of 10 and above, as evidenced by gel electrophoresis. P(BocAEAEMA) was then chain-extended with a model sugar monomer, mannose-acrylate (ManAc), to yield P(AEAEMA)-b-P(ManAc) block copolymers, to potentially provide cell-recognition ability to the polyplex particles. Although the presence of the P(ManAc) block partially inhibited the interaction of P(AEAEMA) with DNA, P(AEAEMA)13-b-P(ManAc)7 was able to form polyplexes with DNA at N/P ratios ranging between 20/1 and 2/1. Dynamic light scattering measurements showed that while P(AEAEMA) (M n = 5.5 kDa) and DNA formed polyplex particles having a hydrodynamic diameter (Dh) of 125 ± 51 nm, P(AEAEMA)13-b- P(ManAc)7 and DNA formed particles with a smaller Dh of 38 ± 10 nm.Article Citation - WoS: 4Citation - Scopus: 6Absorption Spectrum of Monomeric Pseudoisocyanine: a New Perspective and Its Implications for Formation and Spectral Response of J-Aggregates in Solution and in Thin Films(Elsevier Ltd., 2008) Gülen, Demet; Özçelik, SerdarWe argued against the current spectral assignment for absorption spectrum of monomeric PIC which is widely accepted since the pioneering works of Scheibe and Jelley [G. Scheibe, Angew. Chem. 49 (1936) 563; E.E. Jelly, Nature 138 (1936) 1009]. A new spectrum is presented along with its conceptual basis. The hypothesized spectrum attributes the previous 0-0 (≈525 nm) and 0-1 (≈490 nm) assignments, respectively, to intermediates acting as the precursor of J-aggregates and to the 0-0 transition of monomeric PIC and brings the spectrum in accord with the seemingly universal spectral fingerprint of cyanines. The hypothesis is used to analyze and interpret the temperature dependence of the UV-vis absorption of PIC aggregates in saline aqueous solution by incorporating the J-band simulations within frenkel exciton formalism. Its implications for aggregate formation kinetics are given on the basis of current spectroscopic evidence. The hypothesis readily answers several long-standing questions: Why compared to many other cyanines at least an order of magnitude higher dye concentration is needed to form J-aggregates of PIC? Why are there no precursors, since aggregation is expected to be a consecutive process? A large number of observations on steady-state and time-resolved spectral properties, and aggregation kinetics in solution/thin films are likely to find reasonable explanations within this hypothesis.
