Sharif Digital Repository

The polysaccharide, kappa-carrageenan (κC) was chemically modified to achieve a novel superabsorbent hydrogel via graft copolymerization of methacrylamide (MAM) onto the substrate followed by alkaline hydrolysis. Ammonium persulfate (APS) and N,N′-methylene bisacrylamide (MBA) were used as a free-radical initiator and a crosslinker, respectively. The saponification reaction was carried out using sodium hydroxide aqueous solution. Either κC-g-PMAM or hydrolyzed κC-g-PMAM (PMAM: polymethacrylamide) was characterized by FT-IR spectroscopy. The effect of grafting variables (i.e. concentration of MBA, MAM, and APS) and alkaline hydrolysis conditions (i.e. NaOH concentration, hydrolysis time and... 

To synthesize a novel biopolymer-based superabsorbent hydrogel, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) was grafted onto kappa-carrageenan (KC) backbones. The graft copolymerization reaction was carried out in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator, N,N,N',N'-tetramethyl ethylenediamine (TMEDA) as an accelerator, and N,N'-methylene bisacrylamide (MBA) as a crosslinker. A proposed mechanism for KC-g-AMPS formation was suggested and the hydrogel structure was confirmed using FTIR spectroscopy. The affecting variables on swelling capacity, i.e., the initiator, the crosslinker, and the monomer concentration, as well as reaction temperature,... 

Free Content Selective synthesis of conjugated enynes from α-arylalkynols using LiCl-Acidic Al2O3 under solvent-free conditions  

7H-benzimidazo[2,1-a]benz[de]isoquinolin-7-one compounds were prepared in a selective manner by reaction between o-phenylenediamines and appropriate 1,8-naphthalenedicarboxylic anhydrides using acidic alumina under microwave irradiation  

In this study, a series of highly swelling hydrogels based on sodium alginate (NaAlg) and polymethacrylamide (PMAM) was prepared through free radical polymerization. The graft copolymerization reaction was performed in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator andN,N′-methylenebisacrylamide (MBA) as a crosslinker. The crosslinked graft copolymer, alginate-graft-polymethacrylamide (Alg-g-PMAM), was then partially hydrolyzed by NaOH solution to yield a hydrogel, hydrolyzed alginate-graft-polymethacrylamide (H-Alg-g-PMAM). During alkaline hydrolysis, the carboxamide groups of Alg-g-PMAM were converted into hydrophilic carboxylate anions. Either the... 

γ-Alumina is used to catalyze the Cannizzaro reaction in the absence of any base under microwave irradiation in high yields. In the case of terephthalaldehyde the reaction is carried out with high selectivity  

Monomer grafting, a unique technique for polysaccharide modification, is always performed under inert (e.g., N2) atmosphere. This work is the first report related to evaluating the possibility and efficiency of the grafting of acrylonitrile (AN) onto starch in presence of oxygen. Thus, corn starch (in both granular and gelatinized states) as well as soluble starch were grafted by AN using a ceric-carbohydrate redox initiating system. Graft copolymerizations were performed under nitrogen, air, and oxygen atmospheres at similar conditions. Grafting occurrence was verified using chemical and spectral proofs. The polymerization mechanism and kinetics were investigated by recording the... 

The coordination geometries, electronic features, absolute metal ion affinities, geometrical multiplicity and binding strength for the complexes formed by Mg2+, Ca2+, Zn2+ and Cu+ with cytidine and deoxycytidine have been determined theoretically employing the hybrid B3LYP exchange-correlation functional and using 6-311++G(d,p) orbital basis sets. Our study shows that the most stable coordination modes of cytosine nucleosides with these cations are rather similar. In the isolated state, the most stable form corresponds to a tridentate complex in which the cation interacts with three oxygen atoms: one from the carbonyl oxygen of cytosine moiety and two from the sugar unit (i.e., O5′ and O4′).... 

Polymer supported reagents have found many applications in recent years. Scientists in research laboratories of agrochemical and pharmaceutical industries now routinely utilize these compounds to prepare ensembles of small organic molecules for screening. This review is aimed to highlight some of the most important applications of these promising materials in organic synthesis. Furthermore, an extensive listing of polymeric reagents that were recently used in organic synthesis is included. © Springer-Verlag 2007  

As the first part of a continued research on conversion of carboxymethyl cellulosesodium salt (CMC) to useful biopolymer-based materials, large numbers of cyanide functional groups were introduced onto CMC by grafting with polyacrylonitrile (PAN). The graft copolymerization reactions were carried out under nitrogen atmosphere using ceric ammonium nitrate (CAN) as an initiator. Evidence of grafting was obtained by comparing FTIR spectra of CMC and the graft copolymer as well as solubility characteristics of the products. The synthetic conditions were systematically optimized through studying the effective factors including temperature and concentrations of initiator, acrylonitrile monomer,... 

A pH-responsive drug delivery system based on core shell structure of mesoporous silica nanoparticle (MSN) and chitosan-PEG copolymer was prepared and characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), and high-resolution transmission microscope (HR-TEM) techniques. In order to improve compatibility MSN and drug, mesoporous nanosilica was modified by 3-aminopropyl triethoxysilane. The release of erythromycin (a macrolide antibiotic) as a model drug was investigated in two pHs, 7.4 and 5.5  

Chitosan was modified with polyacrylonitrile (PAN) through ceric-initiated graft copolymerization. The chitosan-g-PAN product was saponified using sodium hydroxide aqueous solution to prepare a novel superabsorbent hydrogel, H-chitoPAN. Duration of completing the saponification reaction as well as the water absorbency capacity of the hydrogel was decreased with increasing the alkaline concentration. Either chitosan-g-PAN or H-chitoPAN was characterized by FTIR spectroscopy and DSC, TGA, and DTG thermal methods. According to FTIR, all the nitrile groups were converted to carboxylate and carboxamide groups. Both modified chitosans exhibited enhanced thermal stability over chitosan. The... 

Novel types of highly swelling hydrogels (superabsorbent) were prepared by grafting crosslinked poly acrylic acid-co-2-hydroxyethylmetacrylate (PAA-co-HEMA) chains onto starch through a free radical polymerization method. The effect of grafting variables (i.e., concentration of methylenebisacrylamide (MBA), acrylic acid/2-hydroxy methymetacrylate (AA/HEMA) weight ratio, ammonium persulfate (APS), starch, neutralization percent, were systematically optimized to achieve a hydrogel with a maximum swelling capacity. The superabsorbent (SAP) formation was confirmed by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The controlled-release behavior of... 

Gas-phase acidities of nucleosides, combined with the knowledge of deprotonation sites, could improve our understanding of chemical reactions to biological systems. In this paper, we mainly focus our attention on the influence of cation coordination on acidities of multiple sites in cytosine nucleosides. The acidities of multiple sites in M +-L (where L represents cytosine nucleosides and M + is an alkali metal ion, including Li +, Na + and K +) complexes have been investigated theoretically, employing B3LY P6-311++G(d,p) basis sets. The geometrical characters, gas-phase acidities, sugar puckering and electronic properties of non-deprotonated and/or deprotonated complexes have been... 

A magnetic nanoparticle@starch-g-poly(vinyl sulfate) nanocomposite (MNP@St-g-PVS) as a new magnetic nano-adsorbent has been prepared based on graft copolymerization of vinyl acetate onto starch in the presence of magnetic nanoparticles, where the acetate groups were converted to hydroxyl groups followed by the sulfation of the hydroxyl groups using chlorosulfonic acid. Characterization of this magnetic nanocomposite was carried out by FTIR, TGA, XRD, VSM, SEM, TEM and elemental analysis. The resulting nanocomposite was used as an adsorbent for the removal of typical cationic dyes, methylene blue (MB) and malachite green (MG), from aqueous solutions. All experimental parameters that can... 

Abstract: In the present paper, an efficient Cu-catalyzed regioselective acylation of indoles with phenylglyoxals was developed which is the first example of indolyl diketones synthesis by a heterogeneous catalyst. The magnetic polyacrylonitrile was synthesized through anchoring acrylonitrile monomers on Fe3O4 nanoparticles surface and then modified with 2-aminopyridine. At the final step, copper nanoparticles were immobilized onto the polymeric support containing stable ligands from functionalized nitrile groups of polyacrylonitrile. The different techniques such as Fourier transmission infrared spectroscopy, X-ray diffraction, Field emission scanning electron microscopy, Transmission... 

Abstract: In the present paper, an efficient Cu-catalyzed regioselective acylation of indoles with phenylglyoxals was developed which is the first example of indolyl diketones synthesis by a heterogeneous catalyst. The magnetic polyacrylonitrile was synthesized through anchoring acrylonitrile monomers on Fe3O4 nanoparticles surface and then modified with 2-aminopyridine. At the final step, copper nanoparticles were immobilized onto the polymeric support containing stable ligands from functionalized nitrile groups of polyacrylonitrile. The different techniques such as Fourier transmission infrared spectroscopy, X-ray diffraction, Field emission scanning electron microscopy, Transmission... 

In this study, a new magnetic nanocomposite was synthesized via radical polymerization of methyl acrylate onto modified magnetic nanoparticles followed by the functionalization of the methyl ester groups with ethylenediamine and sodium chloroacetate. The generated magnetic nanocomposite was characterized by FT-IR, TEM, SEM, TGA, VSM, XRD and elemental analysis. Its key role as an adsorbent for the removal of typical cationic dyes, methyl violet and malachite green was investigated in terms of pH, contact time and initial dye concentration. The resulted adsorbent displays excellent adsorption capacities for cationic dyes which are more effective than most of the adsorbents reported so far.... 

A new magnetic nano-adsorbent was synthesized via the radical polymerization of methyl acrylate on modified Fe3O4 nanoparticles, followed by its functionalization by amidation of the methyl ester groups using pentaethylenehexamine, to create active adsorption sites for removing anionic dyes from aqueous media. Physicochemical properties of the adsorbent were then characterized by SEM, TEM, XRD, FTIR, TGA and CHN analysis. The prepared nanocomposite was used as adsorbent for the removal of anionic dyes, naphthol green B and chromeazurol S, from aqueous solution and assessed in view of the kinetics and isotherm adsorption, and the effect of solution pH, contact time and initial dye... 

Density functional theory (DFT) calculations were performed at the B3LYP level with a 6-311++G(d,p) basis set to systematically explore the geometrical multiplicity and binding strength for complexes formed by Li+, Na+, and K+ with cytidine and 2′-deoxycytidine. All computational studies indicate that the metal ion affinity (MIA) decreases from Li+ to Na+ and K+ for cytosine nucleosides. For example, for cytidine the affinity for the above metal ions are 79.5, 55.2, and 41.8 and for 2′-deoxycytidine, 82.8, 57.4, and 42.2 kcal/mol, respectively. It is also interesting to mention that linear correlations between calculated MIA values and the atomic numbers (Z) of the above metal ions were...