Ayfer Menteş

Synthesis and characterization of water soluble O-carboxymethyl chitosan Schiff bases and Cu(II) complexes.

In this study, mono-imine was synthesized (3a and 4a) via a condensation reaction between 2,4-pentadion and aminobenzoic acid (meta or para) in alcohol (1:1). The second-imine (CS-3a and CS-4a) was obtained as a result of the reaction of the free oxo groups of mono-imine (3a and 4a) with the amino groups on the chitosan (CS). Their structures were characterized with FTIR and (13)C CP-MAS. Then, the water soluble forms of CS-3a and CS-4a were obtained through oxidation of the hydroxide groups on the chitosan to carboxymethyl groups using monochloracetic acid ([O-CMCS-3a] · 2H2O and [O-CMCS-4a] · 2H2O). Thus, the solubility problem of chitosan in an aqueous media was overcome and Cu(II) complexes could be synthesized more easily. Characterization of the synthesized O-carboxymethyl chitosan Schiff base derivatives and their metal complexes, [O-CMCS-3a-Cu(OAc)2] · 2H2O and [O-CMCS-4a-Cu(OAc)2] · 2H2O, was conducted using FTIR, UV-Vis, TG/DTA, XRD, SEM, elemental analysis, conductivities and magnetic susceptibility measurements.

Physicochemical comparison of chitin and chitosan obtained from larvae and adult Colorado potato beetle (Leptinotarsa decemlineata)

Chitins and chitosans obtained from larva and adult Colorado potato beetles (Leptinotarsa decemlineata) were physico-chemically characterized and differences between adults and larvae were identified. The dry weight chitin contents of the adult Colorado potato beetles and larvae were determined as 20% and 7%, respectively. The chitin produced chitosan yields of 72% from the adult Colorado potato beetles and 67% from the larvae. FTIR analysis showed that the isolated chitins were in the alpha form. Crystalline index values, determined by XRD, were 72% for larvae and 76% for adults. The degradation temperatures of the isolated chitin structures were measured by TGA, and this showed that the chitin from adult Colorado potato beetles had a more stable structure than that from the larvae. The surface morphologies of the isolated chitin and chitosan structures were analysed with SEM and it was revealed that these structures consisted of nanofibres. According to elemental analysis, the purity of chitin and chitosan from adults was greater than that from the larvae. The results of molecular analysis showed that the chitosans from adults (2.722 kDa) and larvae (2.676 kDa) of the Colorado potato beetle have low molecular weights. Antimicrobial and antioxidant activities of both adult and larval chitosans were determined. The adult potato beetle is more appropriate than the larvae as an alternative chitin source because of the fact that its dry weight chitin content, chitosan yield and purity of chitin are higher than those from the larvae, and its antimicrobial and antioxidant activities are also higher than those from the larvae.

New Chitin, Chitosan, and O-Carboxymethyl Chitosan Sources from Resting Eggs of Daphnia longispina (Crustacea); with Physicochemical Characterization, and Antimicrobial and Antioxidant Activities

The paper describes the isolation and characterization of chitin and chitosan from Daphnia longispina resting eggs harvested from a reservoir. Resting eggs are fertilized eggs that are encased in chitinous shells called ‘ephippia’ and which ensure the survival of the Daphnia population in adverse conditions. The chitin-content of D. longispina resting eggs was found to be 23 ∼ 25% and the chitosan (having a 70 ∼ 75% deacetylation degree) yield of the chitin was 76 ∼ 77%. This high chitin-content indicates that D. longispina resting eggs can be exploited as a chitin source. The structure and thermal properties of chitin, extracted from D. longispina resting eggs, were characterized by employing Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy. The crystallinity of the chitin was found to be very low (48%). Physicochemicallycharacterized chitosan and the produced O-carboxymethyl chitosan were tested for their antimicrobial and antioxidant activity. It has been observed that chitosan displays antimicrobial activity against all pathogenic bacteria, whereas O-carboxymethyl chitosan only exhibits inhibition activity against L. garvieae, L. Monocytogenes ATCC 7644, Y. enterocolitica NCTC 11175 and S. aureus ATCC 25923. In a free radical scavenging activity assay, the IC50 values of chitosan, O-carboxymethyl chitosan and butylated hydroxytoluene were found to be 23.01, 56.43 and 0.05, respectively. The ferric-reducing power of O-carboxymethyl chitosan (EC50 = 8.30) indicated higher activity than chitosan (EC50 = 10.12).

Cu(II) and Pd(II) complexes of water soluble O-carboxymethyl chitosan Schiff bases: Synthesis, characterization.

This study reports the synthesis of two new water soluble O-carboxymethyl chitosan Schiff bases (OCMCS-5 and OCMCS-6a) and their Cu(II) and Pd(II) complexes. Characterizations of these complexes were carried out with FTIR, elemental analysis, (13)C CPMAS, UV-vis, magnetic moment and molar conductivity techniques. The degrees of substitution (DS) for OCMCS-5a and OCMCS-6a were determined to be 0.48 and 0.44 in elemental analysis. The solubility test revealed that OCMCS-5a and OCMCS-6a dissolved thoroughly in water. The surface morphologies of chitosan (CS), OCMCS-5a, OCMCS-6a and their complexes were studied with SEM-EDAX. Thermal stability of the synthesized compounds was evaluated by TG/DTG and their crystallinity values were investigated with powder X-ray diffraction. Cu(II) and Pd(II) contents of the complexes were estimated with ICP-OES. The characterization studies demonstrated that the thermal stability and crystallinity values of the OCMCS-5a and OCMCS-6a were lower than those of CS.

Synthesis, characterization, and catalytic activity in Suzuki coupling and catalase-like reactions of new chitosan supported Pd catalyst.

The aim of this study is to analyze the synthesis of a new chitosan supported Pd catalyst and examination of its catalytic activity in: Pd catalyst was synthesized using chitosan as a biomaterial and characterized with FTIR, TG/DTG, XRD, (1)H NMR, (13)C NMR, SEM-EDAX, ICP-OES, Uv-vis spectroscopies, and magnetic moment, along with molar conductivity analysis. Biomaterial supported Pd catalyst indicated high activity and long life time as well as excellent turnover number (TON) and turnover frequency (TOF) values in Suzuki reaction. Biomaterial supported Pd catalyst catalyzed H2O2 decomposition reaction with considerable high activity using comparatively small loading catalyst (10mg). Redox potential of biomaterial supported Pd catalyst was still high without negligible loss (13% decrease) after 10 cycles in reusability tests. As a consequence, eco-friendly biomaterial supported Pd catalyst has superior properties such as high thermal stability, long life time, easy removal from reaction mixture and durability to air, moisture and high temperature.

Highly efficient, quick and green synthesis of biarlys with chitosan supported catalyst using microwave irradiation in the absence of solvent.

The aim of this study was to develop a quick reaction that had high activity with a small amount of catalyst, which could be an eco-friendly alternative technique for the synthesis of biarlys in Suzuki coupling reactions. First, a novel chitosan Schiff base supported Pd(II) catalyst was synthesized, and its structure was illuminated with FTIR, (1)H NMR, (13)C NMR, TG/DTG, SEM/EDAX, XRD, ICP-OES, UV-vis, magnetic moment, and molar conductivity techniques. Subsequently, the catalytic activity of the catalyst was tested in Suzuki C-C reactions under microwave irradiation using a solvent-free reaction condition. The catalytic tests showed an excellent activity with a small load of the catalyst (0.02 mol%) in 4 min. The catalyst showed seven runs without loss of activity, and high values of turnover numbers (TON) and turnover frequency (TOF) were obtained. The novel biopolymer supported Pd(II) catalyst provided much faster reaction times, higher yields, and reusability under microwave heating compared to classic heating methods.

Green heterogeneous Pd(II) catalyst produced from chitosan-cellulose micro beads for green synthesis of biaryls.

In green catalyst systems, both the catalyst and the technique should be environmentally safe. In this study we designed a green palladium(II) catalyst for microwave-assisted Suzuki CC coupling reactions. The catalyst support was produced from biopolymers; chitosan and cellulose. The catalytic activity of the catalyst was tested on 16 substrates in solvent-free media and compared with those of commercial palladium salts. Reusability tests were done. The catalyst was also used in conventional reflux-heating system to demonstrate the efficiency of microwave heating method. We recorded high activity, selectivity and excellent TONs (6600) and TOFs (82500) just using a small catalyst loading (1.5×10(-3)mol%) in short reaction time (5min). The catalyst exhibited a long lifetime (9 runs). The findings indicated that both green chitosan/cellulose-Pd(II) catalyst and the microwave heating are suitable for synthesis of biaryl compounds by using Suzuki CC coupling reactions.

Design and application of sporopollenin microcapsule supported palladium catalyst: Remarkably high turnover frequency and reusability in catalysis of biaryls

Bio-based catalyst support materials with high thermal and structural stability are desired for catalysts systems requiring harsh conditions. In this study, a thermally stable palladium catalyst (up to 440°C) was designed from sporopollenin, which occurs naturally in the outer exine layer of pollens and is widely acknowledged as chemically very stable and inert biological material. Catalyst design procedure included (1) extraction of sporopollenin microcapsules from Betula pendula pollens (∼25μm), (2) amino-functionalisation of the microcapsules, (3) Schiff base modification and (4) preparation of Pd(II) catalyst. The catalytic activity of the sporopollenin microcapsule supported palladium catalyst was tested in catalysis of biaryls by following a fast, simple and green microwave-assisted method. We recorded outstanding turnover number (TON: 40,000) and frequency (TOF: 400,000) for the catalyst in Suzuki coupling reactions. The catalyst proved to be reusable at least in eight cycles. The catalyst can be suggested for different catalyst systems due to its thermal and structural durability, reusability, inertness to air and its eco-friendly nature.

Production of novel palladium nanocatalyst stabilized with sustainable chitosan/cellulose composite and its catalytic performance in Suzuki-Miyaura coupling reactions

In this study, we designed a new palladium nanocatalyst on chitosan/cellulose composite for the first time to increase the use of sustainable polysaccharides, which are cheap, non-toxic, environmental friendly, abundant in nature, and can be used as support materials for metallic nanoparticles. Physicochemical characterization of fabricated palladium nanocatalyst was illuminated with FT-IR, TG/DTG, SEM/EDAX, XRD, and ICP-OES analyses. Pd nanoparticles were found to be almost spherically structured, and the average particle size was 26-30nm. Then catalytic performance of the designed nanocatalyst was investigated in the synthesis of a series of biphenyl compounds via the Suzuki-Miyaura reaction by using the green method which is conducted in a very short-time, under low temperature, and without the presence of any toxic chemical solvents (e.g., 5min treatment in microwave oven at 400W at 50°C). As a result of the tests, palladium nanocatalyst showed excellent catalytic performance with high conversion yields for a wide range of substrates and with a very low catalyst loading for the Suzuki reactions. Sustainability performance of palladium nanocatalyst was also studied, and it is found that the catalyst was able to be recycled for eight successive runs.

Cationic palladium(II) catalysts on O-carboxymethyl chitosan Schiff base for Suzuki coupling reactions

ABSTRACT In this study, catalytic activity of two different cationic O-Carboxymethyl chitosan Schiff base palladium (II) complexes in Suzuki coupling reactions and synthesis of biarlys having different functional groups, and reusability of the catalysts were tested. Chemical structures of the synthesized biaryls were elucidated by GC-MS and 1H-NMR; and no by-products were observed in the spectra. Cationic palladium (II) catalysts high turnover numbers and selectivity were recorded for the reactions. Mercury test demonstrated that the reaction mechanism proceed a homogeneous route. Reusability tests of cationic biocatalysts showed that their catalytic activity were still highly efficient even after six cycles.