Sidik Silong

Preparation and characterization of poly(amidoxime) chelating resin from polyacrylonitrile grafted sago starch

The preparation of a chelating ion-exchange resin containing amidoxime functional group was carried out by polyacrylonitrile (PAN) grafted sago starch. The PAN grafted copolymer was obtained by free-radical initiating process using ceric ammonium nitrate as an initiator. Conversion of nitrile groups of the grafted copolymer into the amidoxime was carried out by treatment with hydroxylamine under alkaline solution. The chelating poly(amidoxime) resin was characterized by FT-IR spectra, TG and DSC analyses. The chelating behavior of the prepared resin was carried out by using some metal ions. A significant binding property of metal ions by the chelating resin was observed and the maximum copper capacity was 3.0 mmol g ˇ1 at pH 6. The sorption capacities of metal ions by the resin were pHdependent, and its selectivity towards these metal ions is in the following order: Cu 2a >F e 3a >A s 3a >Z n 2a > Ni 2a >C d 2a >C o 2a >C r 3a >P b 2a . The rate of exchange was rapid, i.e. t1=2 < 9 min, based on the exchange of copper

Graft copolymerization of methyl acrylate onto sago starch using ceric ammonium nitrate as an initiator

The graft copolymerization of methyl acrylate onto sago starch was carried out by a free radical initiating process. The free radicals were produced by the chemical initiation method in which ceric ammonium nitrate was used as an initiator. It was found that the percentages of grafting, grafting efficiency, and rate of grafting were all dependent on the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU), mineral acid (H2SO4), and reaction temperature and period. The variables affecting the graft copolymerization were thoroughly examined. The optimum yield of grafting was obtained when the concentration of CAN, MA, AGU, and H2SO4 were used at 8.77 × 10−3, 0.803, 0.135, and 0.175 mol L−1, respectively. The optimum reaction temperature and period were 50°C and 60 min, respectively. The rate of graft polymerization was explored on the basis of experimental results and reaction mechanism. The evidence of grafted copolymers was investigated by using FTIR spectroscopy, TG, and DSC analysis.

Complexes of a tridentate ONS Schiff base. Synthesis and biological properties

Several new complexes of a tridentate ONS Schiff base derived from the condensation of S-benzyldithiocarbazate with salicylaldehyde have been characterised by elemental analyses, molar conductivity measurements and by i.r. and electronic spectra. The Schiff base (HONSH) behaves as a dinegatively charged ligand coordinating through the thiolo sulphur, the azomethine nitrogen and the hydroxyl oxygen. It forms mono-ligand complexes: [M(ONS)X], [M=NiII, CuII, CrIII, SbIII, ZnII, ZrIV or UVI with X = H2O, Cl]. The ligand produced a bis-chelated complex of composition [Th(ONS)2] with ThIV. Square-planar structures are proposed for the NiII and CuII complexes. Antimicrobial tests indicate that the Schiff base and five of the metal complexes of CuII, NiII, UVI, ZnII and SbIII are strongly active against bacteria. NiII and SbIII complexes were the most effective against Pseudomonas aeruginosa (gram negative), while the CuII complex proved to be best against Bacillus cereus (gram positive bacteria). Antifungal activities were also noted with the Schiff base and the UVI complex. These compounds showed positive results against Candida albicans fungi, however, none of them were effective against Aspergillus ochraceous fungi. The Schiff base and its zinc and antimony complexes are strongly active against leukemic cells (CD50 = 2.3–4.3 μg cm−3) while the copper, uranium and thorium complexes are moderately active (CD50 = 6.9–9.5 μg cm−3). The nickel, zirconium and chromium complexes were found to be inactive.

Synthesis and mesomorphic properties of nonsymmetric liquid crystalline dimers containing azobenzene groups

Four novel nonsymmetric dimers containing azobenzene mesogenic groups were synthesized. The nonsymmetric dimers compounds namely, ethyl 4-[(4-{4-(4-((4-nitrophenyl)diazenyl)phenoxy)alkyloxy}phenyl)diazenyl]benzoate were obtained from the alkylation of ethyl 4-[(4-(4-bromoalkyloxy)phenyl)diazenyl]benzoate with 4-[(4-nitrophenyl)diazenyl]phenol. The mesomorphic properties of the compounds were determined by DSC and polarizing optical microscopy. The first member of the series was nonliquid crystalline while all other homologues display nematic and smectic A phases. The trans-azobenzene groups of the dimers display a high-intensity π–π* transition at about 365 nm and a low-intensity n–π* transition at around 465 nm, therefore, photochromism can be achieved by the introduction of the azo linkage to the dimeric liquid crystalline molecules.

Coordination chemistry and biological activity of bidentate and quadridentate nitrogen–sulfur donor ligands and their complexes

The ligand S-benzyldithiocarbazate (SBDTC) acts as a bidentate sulfur–nitrogen chelating agent. The reaction of SnII or SbIII with SBDTC under alkaline conditions gives complexes of composition [Sn(SBDTCA)2] · 2H2O and [Sb(SBDTCA)Cl2 · 2H2O]. A quadridentate Schiff base of SBDTC with benzil, having a donor sequence SNNS, yields complexes, [Cd(SNNS)] and [Zr(O)(SNNS) · H2O]. The ligands and the complexes have been characterized by elemental analyses, i.r., u.v.–vis., molar conductance measurements and 1H-n.m.r. spectroscopy. SBDTC, SnII and SbIII complexes and the SNNS Schiff base together with its CdII and ZrIV complexes display significant antifungal, antibacterial and anti-cancer activity. The SnII complex and the SNNS free Schiff base were very effective against Melanoma (skin cancer cells). The SBDTC and its SnII complex were also very effective against Renal carcinoma (kidney cancer cells). The results have been compared with those of the uncomplexed metal salts and the free ligands. The minimum concentrations for the evaluation of the above activities for CD50 of the samples were in the 1.0–15 μg cm−3 range.

Kinetics and mechanism of free radical grafting of methyl acrylate onto sago starch

The graft copolymerization was carried out by methyl acrylate with sago starch in which ceric ammonium nitrate was used as an initiator. It has been found that the rates of graft polymerization and grafting efficiency were dependent upon the concentration of ceric ammonium nitrate (CAN), methyl acrylate (MA), sago starch (AGU, anhydro glucose unit), mineral acid (H2SO4), and as well as reaction temperature and period. A rate equation of polymerization was established from the proposed reaction mechanism, and the rate of polymerization (Rp) was the first-order dependence of the MA monomer concentration and square root of the CAN concentration. A new kinetic model of the grafting reaction has been proposed, and a normal kinetics of methyl acrylate polymerization was observed. An equation of a predicted model relating the graft fraction of poly(methyl acrylate) with the sago starch has been derived, and validity of the predicted model was verified by the experimental results.

Metal ions binding by chelating ligands from new polymer bearing amidoxime functional groups

A new polymer bearing amidoxime chelating resin was prepared from polyacrylonitrile (PAN) grafted sago starch and the significant binding capacity of metal ions by the resin was observed with a rapid sorption rate.

Benzyl and Methyl Fatty Hydroxamic Acids Based on Palm Kernel Oil as Chelating Agent for Liquid-Liquid Iron(III) Extraction

Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO3 and H2SO4. The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III).

Enzymatic synthesis of fatty hydroxamic acid derivatives based on palm kernel oil.

Fatty hydroxamic acid derivatives were synthesized using Lipozyme TL IM catalyst at biphasic medium as the palm kernel oil was dissolved in hexane and hydroxylamine derivatives were dissolved in water: (1) N-methyl fatty hydroxamic acids (MFHAs); (2) N-isopropyl fatty hydroxamic acids (IPFHAs) and (3) N-benzyl fatty hydroxamic acids (BFHAs) were synthesized by reaction of palm kernel oil and N-methyl hydroxylamine (N-MHA), N-isopropyl hydroxylamine (N-IPHA) and N-benzyl hydroxylamine (N-BHA), respectively. Finally, after separation the products were characterized by color testing, elemental analysis, FT-IR and 1H-NMR spectroscopy. For achieving the highest conversion percentage of product the optimum molar ratio of reactants was obtained by changing the ratio of reactants while other reaction parameters were kept constant. For synthesis of MFHAs the optimum mol ratio of N-MHA/palm kernel oil = 6/1 and the highest conversion was 77.8%, for synthesis of IPFHAs the optimum mol ratio of N-IPHA/palm kernel oil = 7/1 and the highest conversion was 65.4% and for synthesis of BFHAs the optimum mol ratio of N-BHA/palm kernel oil = 7/1 and the highest conversion was 61.7%.

Copper ion extraction by a mixture of fatty hydroxamic acids synthesized from commercial palm olein

Abstract A mixture of fatty hydroxamic acids (FHA), synthesized from a commercial palm olein, was evaluated as an extractant for extraction of copper ion from aqueous media. The content of hydroxamic acid groups in the FHA, analyzed by elemental analysis, was 3.52 mmol/g. Copper extraction from aqueous media was studied by solvent extraction technique using octanol as an organic phase. The extraction of copper ion was through the formation of 1∶2 (Cu(II)∶FHA) complex, pH dependent and not affected by the presence of a large amount of Co(II), Ni(II), Cd(II) and Zn(II) ions.