Thermal, X-ray diffraction and electronic spectral studies of gamma irradiated nickel(II) complexes of ethylenediamine, triethylenetetramine and o-toluidine

Thermal decomposition, X-ray diffraction and electronic spectra of nickel(II) complexes of ethylenediamine, triethylenetetramine and o-toluidine were studied before and after γ-irradiation. Irradiation enhanced thermal decomposition lowering thermal and kinetic parameters. From X-ray diffraction studies, unirradiated and irradiated complexes are found to be orthorhombic. A change in lattice parameters was observed upon irradiation. The parameters Dq, β and B^I were calculated from the UV–visible spectra of the complexes. Irradiation decreased Ligand Field Stabilisation Energies (LFSE) (Dq) and increased Racah parameter B^I and the covalency factor β of the complexes.     

Metal adsorption of carboxymethyl cellulose/carboxymethyl chitosan blend hydrogels prepared by Gamma irradiation

Blend hydrogels based on the carboxymethyl cellulose (CMC) and carboxymethyl chitosan (CMCts) were prepared by γ-irradiation of a high concentrated CMC/CMCts aqueous solution. Properties of the hydrogels, such as gel fraction, swelling ratio, gel strength, and metal adsorption for Pb and Au were investigated. The gel fraction increased with increasing dose, while the swelling ratio decreased with increasing it. The obtained blend hydrogels had high adsorption performance which was controlled by adjusting the composition of CMC/CMCts.     

Stereoselective total synthesis of (+)-(6R,2′S)-cryptocaryalactone and (−)-(6S,2′S)-epi cryptocaryalactone

The total synthesis of (+)-(6R,2′S)-cryptocaryalactone and (−)-(6S,2′S)-epi cryptocaryalactone is reported based on stereoselective reduction of δ-hydroxy β-keto ester to install 1,3-polyol system, cis Wittig olefination, and lactonization as the key steps. The synthesis of (−)-(6S,2′S)-epi cryptocaryalactone is also reported using syn-benzylidene acetal formation and a preferential Z-Wittig olefination reaction and lactonization as the key steps.     

Effects of gamma irradiation on the shoot length of Cicer seeds

The effects of radiation on the shoot and root lengths of germinated seedling of irradiated seeds of Cicer species, i.e. three kabuli types and four desi types of cultivated chickpea (Cicer arietinum Ladiz.) and 2 annual wild types (C. reticulatum Ladiz. and C. bijugum K.H. Rech.) were investigated. The seeds were irradiated with a ⁶⁰Co gamma source using 0, 200, 300 and 400 Gy doses at 1.66 kGy h⁻¹. At 200 Gy minor effects could be observed, but at 400 Gy an obvious depression of shoot length was observed. The kabuli types were more affected than the desi ones. The critical dose that prevented the shoot and root elongation varied among species and also ranged from genotypes to genotype within species.     

Effect of γ irradiation on the surface properties of wet polysulfone films containing poly(vinylpyrrolidone)

In Japan, hemodialyzers are usually sterilized by γ irradiation. However, the polymer materials used in the dialysis membrane, such as polysulfone (PSf) and poly(vinylpyrrolidone) (PVP), undergo crosslinking or degradation on exposure to γ radiation. In the present study, we prepared PSf/PVP films (PVP content, 0–50 wt%) and used atomic force microscopy (AFM) to perform nanoscale evaluations of the effect of γ irradiation (25 and 50 kGy) on the surface properties of wet PSf/PVP surfaces. Force‐curve measurements were used to evaluate the hardness of and fibrinogen adsorbability on the wet PSf/PVP surface; fibrinogen adsorbability on the wet PSf/PVP surface was evaluated using AFM probes with fibrinogen immobilized on the tips of the probes. At PVP levels greater than 5 wt%, the wet PSf/PVP film surface was completely covered with hydrated and swollen PVP particles. The surface hardness of the wet PSf/PVP films exposed to 25‐kGy γ irradiation greatly decreased with increasing PVP content, whereas the surface hardness of the wet PSf/PVP films exposed to 50‐kGy γ irradiation did not decrease significantly. At higher PVP levels, the reduction in the fibrinogen adsorbability on a wet PSf/PVP film exposed to 25‐kGy γ irradiation was more significant than that on a wet PSf/PVP film exposed to 50‐kGy γ irradiation. PVP particles on the wet PSf/PVP film surface exposed to 50‐kGy γ irradiation did not show significant hydration and swelling because the polymer materials PVP–PSf and PVP‐PVP in these membranes has undergone excessive crosslinking due to γ irradiation. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of γ-irradiation on the morphology and slow crack growth in high-density polyethylene

The effects of γ-irradiation were measured in a HDPE and in the resin after it was recrystallized. The fracture mode of the initial material transformed from crazing to complete brittle failure at a critical dose. The failure mode of the recrystallized material transformed from crazing to shear deformation, which produced an extremely long failure time, and finally, at a higher dose, its fracture became brittle. The relationship between morphology and slow crack growth is presented where crosslinking was the major factor. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1211–1218, 1998     

A study of biodegradation/γ-irradiation on the degradation of p-chloronitrobenzene

A microbial strain, Vagococcus sp. B32, was isolated and applied to degrade p-chloronitrobenzene (p-CNB) in aqueous solutions. Three degradation methods: biodegradation, direct γ-irradiation and ⁶⁰Co-γ pre-irradiation with biodegradation by B32 were carried out. The decrease of p-CNB and the net increase of Cl⁻ were investigated to evaluate the degradation efficiency. The preliminary results showed that the combined method of pre-irradiation with biodegradation of B32 was more effective than the two others.     

Stabilization Effects of Natural Compounds and Polyhedral Oligomeric Silsesquioxane Nanoparticles on the Accelerated Degradation of Ethylene-Propylene-Diene Monomer

In this work the analysis on the stabilization activities of some natural antioxidants (rosemary extract, capsaicin, quercetin or oleanolic acid) is presented. A similar contribution of an inorganic structure—polyhedral oligomeric silsesquioxane (POSS) nanoparticles—is also evaluated. The stabilization effects on the oxidation protection were investigated for several formulations based on ethylene-propylene-diene-terpolymer (EPDM). The samples were examined in pristine state or after γ-irradiation, when the accelerated degradation scission of polymer macromolecules followed by the mitigation of oxidation. Three evaluation procedures: chemiluminescence, FTIR spectroscopy and thermal analysis were applied for the characterization of stability efficiency. The delaying effect of oxidative aging in EPDM matrix is illustrated by the values of activation energy, which are correlated with the type and concentration of embedded compounds. The durability of studied EPDM formulations is discussed for the assessment of material life. The improved behavior of structured hybrids useful for the optimization application regimes is essentially based on the antioxidant properties of polyphenolic components in the cases of natural antioxidants or on the penetration of free radical intermediates into the free volumes of POSS.     

Trimethylsilyl cyanide addition to aldimines and its application in the synthesis of (S)-phenylglycine methyl ester

The addition of TMSCN to a variety of arylaldimines (Strecker reaction) in the presence of LiClO₄ or BF₃·Et₂O in acetonitrile has been studied. The reaction provided the addition products in very high yields. The method has been successfully utilized for the synthesis of (S)-phenylglycine methyl ester.     

Solid phase microextraction for the determination of volatile organics in the foliage of Fraser fir (Abies fraseri)

Solid phase micro extraction (SPME) was investigated for the determination of volatile chemicals in the foliage of Fraser fir (Abies fraseri). Advantages of SPME include its speed, sensitivity, and ability to determine volatiles without chemical solvents. In this study, qualitative comparisons were performed of the volatiles emitted from living foliage (in situ), damaged living foliage (in situ damaged), and severed foliage (ex situ). These studies suggest that β-phellandrene and γ-terpinene may be emitted as a response to foliar injury. Comparisons were made of the volatiles collected by SPME with ex situ sampling to previous studies in our laboratory using methylene chloride extraction. Similar results were obtained by the two extraction methods.     

A novel method for the synthesis of (Z)-α-selenyl-α,β-unsaturated ketones via acylation of (E)-α-selanylvinylstannanes

The (E)-α-selenylvinylstannanes react with acyl halides in presence of a catalytic amount of Pd(PPh₃)₄ to give the corresponding (Z)-α-selenyl-α,β-unsaturated ketones in good yield.     

Oxidation of Tricarbonyl (η1 η2-but-3-en-1-yl)iron(0)and Tricarbonyl (η3-allyl)iron(0) Anion Complexes with Dioxygen

The addition of reactive carbanions to tricarbonyl(η⁴-1,3-diene)iron(0) complexes proceeded at ?78 °C to give putative tricarbonyl(η¹,η²-but-3-en-1-y1)iron(0) anion complexes and at 25 °C to produce postulated tricarbonyl(η³-allyl)iron(O) anion complexes; trapping of reactive intermediates with dioxygen produced γ,δ-unsaturated acids and allylic alcohols, respectively.     

Fluorescence properties of (R)- and (S)-[1,1′-binaphthalene]-2,2′-diols solutions and their complexes with cyclodextrins in aqueous medium

Steady-state and time-resolved fluorescence techniques were used to study (R)- and (S)-[1,1′-binaphthalene]-2,2′-diol (1,1′-binaphthol or BINOL) dilute solutions of different polarity solvents, as well as their inclusion complexes with α- and βcyclodextrins (CDs) in water. BINOLs in dilute water solutions exhibited a surprisingly high fluorescence anisotropy that was explained as being due to the formation of fairly large order π–π stacking aggregates in aqueous polar media. Stoichiometries, formation constants and the changes of enthalpy and entropy upon inclusion were also obtained by measuring the variation of the fluorescence intensity with [CD] and temperature. Results agree with the formation of 1:1 stoichiometry complexes, but the association constants are rather low and very similar for both enantiomers. Molecular mechanic calculations in the presence of water were employed to study the formation of BINOL complexes with both α- and βCDs. For the most stable structures of any of the complexes only a small portion of the guests, in agreement with thermodynamics parameters and quenching experiments, penetrates inside the CD cavities. Driving forces for 1:1 inclusion processes may be dominated by non-bonded van der Waals host:guest interactions. The low guest:host binding constants and poor enantioselectivity of α- and βCDs for BINOLS may be a consequence of the BINOL aggregation in water.     

Poly(L‐lysine) and clay nanocomposite with desired matrix secondary structure: Effects of polypeptide molecular weight

Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007.     

Preparation of Al(OH)3/PMMA nanocomposites by emulsion polymerization

Al(OH)₃/PMMA nanocomposites were prepared by the emulsion polymerization of methyl methacrylate (MMA) in the presence of surface‐functionalized Al(OH)₃ particles. Nanosized Al(OH)₃ particles were previously functionalized with a silane coupling agent, 3‐(trimethoxysilyl) propyl methacrylate (γ‐MPS), which was confirmed by FT‐IR and XRF analysis. The average size of seed particles was around 70 nm, and the density of the coupling agent on the particles was calculated to be 8.9 µmol m^?2. The emulsion polymerization was attempted at relatively high solid content of 40–46 wt%. The ratio of the seed particles to MMA had a strong influence on the stability of latex as well as the morphology of composites. Nanocomposites where several PMMA nodules were attached on the surface of Al(OH)₃ core were produced with stable latex emulsion when the weight percents of Al(OH)₃ to MMA were below 20. In the case of higher ratio of 30%, however, the latexes became unstable with an aggregation, and the product morphology was in the shape of large composite. Thermogravimetric analysis showed an improved thermal stability of PMMA composites with the incorporation of Al(OH)₃ nanoparticles. Copyright © 2008 John Wiley & Sons, Ltd.