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  1. Dag A, Jiang Y, Karim KJ, Hart-Smith G, Scarano W, Stenzel MH
    Macromol Rapid Commun, 2015 May;36(10):890-7.
    PMID: 25790077 DOI: 10.1002/marc.201400576
    The delivery of macromolecular platinum drugs into cancerous cells is enhanced by conjugating the polymer to albumin. The monomers N-(2-hydroxypropyl)methacrylamide (HPMA) and Boc protected 1,3-diaminopropan-2-yl acrylate (Ac-DAP-Boc) are copolymerized in the presence of a furan protected maleimide functionalized reversible addition-fragmentation chain transfer (RAFT) agent. The resulting polymer with a composition of P(HPMA14 -co-(Ac-DAP-Boc)9 ) and a molecular weight of Mn = 7600 g mol(-1) (Đ = 1.24) is used as a macromolecular ligand for the conjugation to the platinum drug. Thermogravimetric analysis reveals full conjugation. After deprotection of the maleimide functionality of the polymer, the reactive polymer is conjugated to albumin using the Cys34 functionality. The conjugation is monitored using size exclusion chromatography, MALDI-TOF (matrix assisted laser desorption ionization time-of-flight), and SDS Page (sodium dodecyl sulphate polyacrylamide gel electrophoresis). The polymer-albumin conjugates self-assemble in water into nanoparticles of sizes of around 80 nm thanks to the hydrophobic nature of the platinum drugs. The albumin coated nanoparticles are readily taken up by ovarian cancer cell lines and they show superior toxicity compared to a control sample without protein coating.
  2. Sutirman ZA, Sanagi MM, Abd Karim KJ, Abu Naim A, Wan Ibrahim WA
    Int J Biol Macromol, 2019 Jul 15;133:1260-1267.
    PMID: 31047925 DOI: 10.1016/j.ijbiomac.2019.04.188
    Grafting of crosslinked chitosan with monomer, N-vinyl-2-pyrrolidone, has been carried out to investigate its adsorption capacity toward Orange G (OG) from aqueous solutions. The adsorption performance of modified chitosan (cts(x)-g-PNVP) was examined and compared with that of the unmodified chitosan. The effects of initial pH, contact time and initial dye concentration were investigated in a batch system. The experimental data were correlated with the Langmuir and Freundlich isotherm models. The maximum adsorption capacity of cts(x)-g-PNVP (63.7mgg-1) based on Langmuir equation was relatively higher than that of the unmodified chitosan (1.7mgg-1). The kinetic studies showed that the adsorption process was consistent with the pseudo-second order kinetic model. Interaction mechanisms between OG and cts(x)-g-PNVP were also proposed. The overall results suggested that the prepared cts(x)-g-PNVP stands a good candidate as adsorbent for removal of anionic dye from aqueous solutions.
  3. Sutirman ZA, Sanagi MM, Abd Karim KJ, Wan Ibrahim WA
    Carbohydr Polym, 2016 Oct 20;151:1091-1099.
    PMID: 27474659 DOI: 10.1016/j.carbpol.2016.06.076
    A new poly(methacrylamide) grafted crosslinked chitosan was prepared for removal of lead, Pb(II) ion from aqueous solution. Crosslinked chitosan, in beads form, was grafted with methacrylamide (MAm) using ammonium persulfate (APS) as free radical initiator. Evidence of grafting was determined by comparing FTIR, TGA, SEM and (13)C NMR analyses of chitosan and graft copolymer. The optimal conditions for grafting reaction were as follow: crosslinked chitosan beads (1g), MAm (17.62×10(-1)M), APS (2.63×10(-1)M), reaction time (3h) and temperature (60°C). The modified chitosan bead was then used in laboratory batch experiments to evaluate the removal of Pb(II) ion from water samples. The Langmuir and Freundlich adsorption models were also applied to describe the equilibrium isotherms. The results revealed that the adsorption of Pb(II) ions onto the beads fitted very well with the Langmuir model with the maximum capacity (qmax) of 250mgg(-1).
  4. Sutirman ZA, Sanagi MM, Abd Karim KJ, Wan Ibrahim WA, Jume BH
    Int J Biol Macromol, 2018 Sep;116:255-263.
    PMID: 29746971 DOI: 10.1016/j.ijbiomac.2018.05.031
    In this study, the Cu(II) and Cd(II) ions removal behavior of crosslinked chitosan beads grafted poly(methacrylamide) (abbreviated as crosslinked chitosan-g-PMAm) from single metal ion solutions was investigated. The modified chitosan beads presented a remarkable improvement in acid resistance. The batch experiments demonstrated that pH of solution played a significant role in adsorption. It was found that the adsorption of Cu(II) and Cd(II) were optimum at pH 4 and pH 5, respectively. The maximum adsorption capacities for Cu(II) and Cd(II) based on Langmuir equation were 140.9 mg g-1 and 178.6 mg g-1, respectively. Pseudo-second order gave a better fit for adsorption data with respect to linearity coefficients than pseudo-first order suggesting that chemisorption or electron transfer is the dominant mechanism of the metal ions onto crosslinked chitosan-g-PMAm. In addition, X-ray photoelectron spectroscopy (XPS) investigations revealed that adsorption of both metal ions took place on the surfaces of crosslinked chitosan-g-PMAm by chelation through CNH2, CO and CO groups. Overall, the modified chitosan has proved a promising adsorbent for removal of metal ions.
  5. Sutirman ZA, Rahim EA, Sanagi MM, Abd Karim KJ, Wan Ibrahim WA
    Int J Biol Macromol, 2020 Jun 15;153:513-522.
    PMID: 32142849 DOI: 10.1016/j.ijbiomac.2020.03.015
    A new crosslinked chitosan grafted with methyl methacrylate (M-CTS) adsorbent was synthesized via free radical polymerization for effective removal of Cu(II) ions from aqueous solution. Crosslinked chitosan (1 g) was grafted with 29.96 × 10-1 M methyl methacrylate in the presence of 2.63 × 10-1 M ammonium persulfate as initiator at 60 °C for 2 h to give grafting and yield percentages of 201% and 67%, respectively. Batch adsorption experiment was performed as a function of solution pH, initial metal ion concentration and contact time. The isotherm data were adequately described by Langmuir model, while kinetic study revealed that the pseudo-second order rate model best fitted for the experimental data. The maximum adsorption capacity for M-CTS at pH 4 was 192.31 mg g-1. Furthermore, the reusability of over six adsorption-desorption cycles suggested that M-CTS is a durable adsorbent and good candidate for metal ions treatment.
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