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Abstract  

In the present communication we report on the radiation induced grafting of methyl methacrylate (MMA) onto irradiated isotactic polypropylene film (IPP) by Peroxidation method to prepared grafted membrane (IPP-g-MMA). The radioactive isotope 60Co was used as the source of gamma radiation. A plausible mechanism of grafting has been proposed. Optimum conditions pertaining to maximum percentage of grafting were evaluated as a function of different reaction parameters such as radiation dose, inhibitor concentration, monomer concentration, reaction time and reaction temperature respectively. Maximum percentage of grafting (85%) was obtained at [radiation dose] = 25 kGy, [inhibitor concentration] = 0.04 wt%, [MMA] = 6 wt%, [Reaction Temperature] = 60 °C in a [Reaction time] of 120 min. The evidence of grafted membrane was characterized by Fourier transform infrared spectroscopy, Atomic force microscopy method, Scanning electron microscopy which indicates that MMA has been grafted onto IPP. Hydrolysis of the grafted membranes in 1 N NaOH transformed ester groups of the grafted membranes to carboxylic acid and hydroxyl groups to form hydrolyzed grafted membranes. Hydrolyzed grafted membranes were investigated for their swelling behavior. Swelling properties of the hydrolyzed grafted membranes were performed in different solvents such as water, N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). Maximum percentage swelling value of IPP-g-MMA was observed in pure DMSO, followed by DMF and water.

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Abstract  

New mixed-ligand complexes with empirical formulae: Mn(2-bpy)1.5L22H2O, M(2-bpy)2L23H2O (M(II)=Co, Cu), Ni(2-bpy)3L24H2O and M(2,4’-bpy)2L22H2O (where 2-bpy=2,2’-bipyridine, 2,4’-bpy=2,4’-bipyridine; L=HCOO ) have been obtained in pure solid-state. The complexes were characterized by chemical and elemental analysis, IR and VIS spectroscopy, conductivity (in methanol and dimethylsulfoxide). The way of metal-ligand coordination discussed. The formate and 2,4’-bpy act as monodentate ligands and 2-bpy as chelate ligand. The new complexes with ligand isomerism were identified. During heating the complexes lose water molecules in one or two steps. Thermal decomposition after dehydration is multistage and yields corresponding metal oxides as final products. A coupled TG-MS system was used to analysis principal volatile thermal decomposition (or fragmentation) products of Ni(2,4’-bpy)2(HCOO)22H2O under dynamic air or argon atmosphere.

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Abstract  

Enthalpies of solution of dibenzo-18-crown-6 at infinite dilution have been measured in tetrachloromethane, benzene, chloroform, pyridine, acetone, dimethylformamide, dimethylsulfoxide, acetonitrile, benzyl alcohol and propylene carbonate at temperature of 298.15 K. Values for enthalpy of solvation and solute–solvent interaction in the solvents were determined. Correlation of enthalpies of solvation with the enthalpy of cavity formation and contribution for the different types of solute–solvent interaction was obtained. In benzene, tetrachloromethane, pyridine, DMF and DMSO polar conformer of DB18C6 dominates. Its effective dipole moment amounts to 3.7 D. Conformation dynamics of the solute reduces the effective polarity of such solvents as acetone, chloroform and propylene carbonate in which population of polar conformer of dibenzo-18-crown-6 decreases. Condensation of two benzene rings to 18-crown-6 results in increasing molecule polarity and exothermic contribution of dipole–dipole interaction in polar solvent media. The specific interaction with acetonitrile and chloroform becomes weaker from 18-crown-6 to dibenzo-18-crown-6.

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Abstract  

An investigation on the thermodynamics of complex formation between Ag(I) ion and two tripodal ligands tris[(2-pyridyl)methyl]amine (TPA) and 6,6′-bis-[bis-(2-pyridylmethyl)aminomethyl]-2,2′-bipyridine (BTPA) has been carried out in the aprotic solvents dimethylsulfoxide (DMSO) and dimethylformamide (DMF) by means of potentiometry and titration calorimetry. The results for TPA are compared with those already obtained for other aliphatic tripodal polyamines. In general, the TPA ligand forms complexes less stable than 2,2′,2″-triaminotriethylamine (TREN) and tris(2-(methylamino)ethyl)amine (Me3TREN) as a result of the combination of higher structural rigidity of TPA and lower σ-donor ability of pyridinic moieties with respect to primary and secondary amines. The same trend is found if the stability of Ag(I) complex with TPA is compared with that of tris(2-(dimethylamino)ethyl)amine (ME6TREN), despite the pyridinic nitrogen is formally a tertiary one. Theoretical calculations run to explain the reasons of this weaker interaction indicate that this difference is due to solvation, rather than to steric or σ-donor effects. The ligand BTPA is able to form bimetallic species whose relative stability is largely influenced by the different solvation of Ag(I) ion in DMSO and DMF rather than by the difference in the dielectric constants of these two media.

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Abstract  

The thermodynamic functions of complex formation of benzo-15-crown-5 ether (B15C5) and sodium cation (Na+) in acetone–water mixtures at 298.15 K have been calculated. The equilibrium constants of B15C5/Na+ complex formation have been determined by conductivity measurements. The enthalpic effect of complex formation has been measured by the calorimetric method. The complexes are enthalpy-stabilized but entropy-destabilized in acetone–water mixtures. The effects of hydrophobic hydration, preferential solvation of B15C5 by a molecule of water and acetone, respectively and the solvation of Na+ on the complex formation processes have been discussed. The calculated thermodynamic functions of B15C5/Na+ complex formation and the effect of benzene ring on the complex formation have been compared with analogous data obtained in dimethylsulfoxide–water mixtures. The effect of carbonyl atom replacement in acetone molecule by sulphur atom (DMSO molecule) on the thermodynamic functions of complex formation has been analysed.

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Abstract  

New mixed-ligand complexes with empirical formulae M(4-bpy)L21.5H2O (M(II)=Mn, Co), Ni(4-bpy)2L2 and Cu(4-bpy) L2H2O (where: 4-bpy=4,4'-bipyridine, L=CC L2HCOO-) have been isolated in pure state. The complexes have been characterized by elemental analysis, ir spectroscopy, conductivity (in methanol, dimethylformamide and dimethylsulfoxide solutions) and magnetic and x-ray diffraction measurements. The Mn(II) and Co(II) complexes are isostructural. The way of metal-ligand coordinations discussed. the ir spectra suggest that the carboxylate groups are bonded with metal(II) in the same way (Ni, Cu) or in different way (Mn, Co). The solubility in water is in the order of 19.4010-31.8810-3ł mol dm-3ł. During heating the hydrate complexes lose all water in one step. The anhydrous complexes decompose to oxides via several intermediate compounds. A coupled TG-MS system was used to analyse the principal volatile products of obtained complexes. The principal volatile products of thermal decomposition of complexes in air are: H2O2 +, CO2 +, HCl+, Cl2 +, NO+ and other.

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Journal of Thermal Analysis and Calorimetry
Authors: Mihaela Badea, Rodica Olar, Dana Marinescu, Valentina Uivarosi, Teodor Nicolescu, and Daniela Iacob

Abstract  

A series of new complexes with mixed ligands of the type RuLm(DMSO)nCl3·xH2O ((1) L: oxolinic acid (oxo), m = 1, n = 0, x = 4; (2) L: pipemidic acid (pip), m = 2, n = 1, x = 2; (3) L: enoxacin (enx), m = 2, n = 1, x = 0; (4) L: levofloxacin (levofx), m = 2, n = 2, x = 8; DMSO: dimethylsulfoxide) were synthesized and characterized by chemical analysis, IR and electronic data. Except oxolinic acid that behaves as bidentate, the other ligands (quinolone derivatives and DMSO) act as unidentate. Electronic spectra are in accordance with an octahedral stereochemistry. The thermal analysis (TG, DTA) in synthetic air flow elucidated the composition and also the number and nature of both water and DMSO molecules. The TG curves show 3–5 well-separated thermal steps. The first corresponds to the water and/or DMSO loss at lower temperatures followed either by quinolone thermal decomposition or pyrolisys at higher temperatures. The final product is ruthenium(IV) oxide.

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Abstract  

The heat effects of the reactions of formation of ethylenediamine-copper(II) complexes were determined calorimetrically in mixtures of water with ethanol, acetone and dimethylsulfoxide. The results were interpreted in terms of the enthalpies of transfer (Δt H 0) of the complex former, the ligand and the complex ion from water to binary solvents. In water—DMSO mixtures, the Δt H 0 values for copper(II) and complex ions were found to change in similar ways, and their contributions to the reaction heat effects compensate each other to a large extent. Thus, the reaction enthalpy change due to solvent composition variation is caused mainly by the changes in ligand solvation enthalpies. In aqueous ethanol and acetone solutions, the changes in Δt H 0 for all reagents influence the heat effect equally.

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Experiments were carried out on sperm cryopreservation of two European percid fish species, the pikeperch (Sander lucioperca) and the Volga pikeperch (S. volgensis) . Two experiments were conducted on pikeperch sperm. In the first, the effects of three extenders (Glucose, KCl, Sucrose) and two cryoprotectants (dimethyl-sulfoxide: DMSO, methanol: MeOH) were tested on motility and fertilization. In the second, the effects of two dilution ratios (1: 1, 1: 9) and two cryoprotectants (DMSO, MeOH) on hatching were investigated. In the experiment on Volga pikeperch the suitability of using cryopreservation for fertilization was investigated. In the first experiment on pikeperch the highest post-thaw motility (28 ± 21%) and fertilization rate (43 ± 12%) was found with DMSO as cryoprotectant in combination with Glucose extender. In the second, the highest hatch rate (41 ± 22%) was observed with MeOH as cryoprotectant and 1: 1 sperm dilution ratio, however no significant difference was found among the results. In the experiment on Volga pikeperch hatch rates with cryopreserved sperm (60 ± 2%) did not significantly differ from the control (60 ± 6%). Contamination of sperm with urine seems to be a key problem in the success of sperm cryopreservation of these species.

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. 3 90 98 Shaw, J. M., Diotallevi, L. and Trounson, A. O. (1991): A simple rapid 4.5 M dimethyl-sulfoxide freezing technique for the cryopreservation

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