Recyclable Polymer-Supported N-Hydroxyphthalimide Catalysts for Selective Oxidation of Pullulan

This paper proposes a convenient route to oxidize the –CH2–OH groups in the water-soluble pullulan, using a new catalytic polymer-supported N-hydroxyphthalimide (NHPI) immobilized on polystyrene. The protocol involves the presence of sodium hypochlorite and sodium bromide. The conversion is possible at room temperature, atmospheric pressure, and pH = 10. The characterization of both the catalysts and oxidized pullulan was done using NMR and FTIR methods. Using polyelectrolyte titration with end-point indication by means of a particle-charge detector (PCD), we were able to assess the degree of electrokinetic charge in all oxidized samples as a consequence of the conversion of the –CH2–OH group into –COOH moieties. The possibility of recovery and recycling of the polymer-supported NHPI catalyst was tested for up to four cycles, since the morphological analyses performed on the catalysts using SEM revealed no significant changes.

[1]  M. Bercea,et al.  Physical Hydrogels of Oxidized Polysaccharides and Poly(Vinyl Alcohol) for Wound Dressing Applications , 2019, Materials.

[2]  S. Coseri,et al.  Cellulose: A ubiquitous platform for ecofriendly metal nanoparticles preparation , 2019, Coordination Chemistry Reviews.

[3]  Baojiao Gao,et al.  Some catalytic characteristics of compositional catalysts of immobilized N-hydroxyphthalimide and metal salts in aerobic oxidation of 1-phenylethanol , 2018, Catalysis Communications.

[4]  M. Iacob,et al.  Carboxylated Polysaccharides Decorated with Ultrasmall Magnetic Nanoparticles with Antibacterial and MRI Properties , 2017 .

[5]  S. Coseri Cellulose: To depolymerize… or not to? , 2017, Biotechnology advances.

[6]  T. Budtova,et al.  Oxidation vs. degradation in polysaccharides: Pullulan – A case study , 2016 .

[7]  Beata Orlińska,et al.  N-Hydroxyphthalimide Immobilized on Poly(HEA-co-DVB) as Catalyst for Aerobic Oxidation Processes , 2016, Catalysis Letters.

[8]  Meng Jian,et al.  Catalytic properties of N-hydroxyphthalimide immobilized on a novel porous organic polymer in the oxidation of toluene by molecular oxygen , 2016 .

[9]  J. Zawadiak,et al.  Polymer-Supported N-Hydroxyphthalimide as Catalyst for Toluene and p-Methoxytoluene Aerobic Oxidation , 2015, Catalysis Letters.

[10]  T. Budtova,et al.  Synthesis, characterization and solution behaviour of oxidized pullulan. , 2014, Carbohydrate polymers.

[11]  K. Edgar,et al.  Synthesis of amphiphilic 6-carboxypullulan ethers. , 2014, Carbohydrate polymers.

[12]  S. Coseri,et al.  Oxidation of Cellulose Fibers Mediated by Nonpersistent Nitroxyl Radicals , 2010 .

[13]  B. Simionescu,et al.  Mild and selective oxidation of cellulose fibers in the presence of N-hydroxyphthalimide. , 2009, Biomacromolecules.

[14]  S. Coseri N‐Hydroxyphthalimide (NHPI)/lead tetraacetate reactions with cyclic and acyclic alkenes , 2009 .

[15]  S. Coseri Phthalimide‐N‐oxyl (PINO) Radical, a Powerful Catalytic Agent: Its Generation and Versatility Towards Various Organic Substrates , 2009 .

[16]  S. Coseri N-Hydroxyphthalimide (NHPI)/Lead Tetraacetate, a Peculiar System for the Phthalimide-N-Oxyl (PINO) Radical Generation. , 2008 .

[17]  T. Leathers Biotechnological production and applications of pullulan , 2003, Applied Microbiology and Biotechnology.

[18]  T. Kimoto,et al.  Safety studies of a novel starch, pullulan: chronic toxicity in rats and bacterial mutagenicity. , 1997, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[19]  H. V. Bekkum,et al.  Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism , 1995 .

[20]  Herman van Bekkum,et al.  Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans , 1995 .

[21]  S. Coseri,et al.  ENALAPRIL MALEATE LOADED PULLULAN FILM FOR MUCOADHESIVE BUCCAL DRUG DELIVERY APPLICATIONS , 2016 .

[22]  S. Coseri,et al.  MILD OXIDATION OF CELLULOSE FIBERS USING DIOXYGEN AS ULTIMATE OXIDIZING AGENT , 2011 .

[23]  C. Arnosti,et al.  Nuclear Magnetic Resonance Spectroscopy of Pullulan and Isomaltose: Complete Assignment of Chemical Shifts , 1995 .