Thermal analysis characterization of PAAm-<Emphasis Type="Italic">co</Emphasis>-MC hydrogels

This paper reports the thermal characterization of polyacrylamide-co-methylcellulose hydrogels and the constituent monomers (acrylamide and methylcellulose). Polymeric materials can be used to produce hydrogels, which can be natural, synthetic, or a mixture. The hydrogels described here were obtained by free radical polymerization, in the presence of N,N′-methylene-bis-acrylamide as a cross-linker agent. Four acrylamide concentrations were used for the synthesis of hydrogels: 3.6, 7.2, 14.7, and 21.7% (w/v). The materials so obtained were analyzed by TG, DTG, DSC, and FT-IR. The TG curves of acrylamide and methylcellulose showed three mass loss events. In DSC curves, the acrylamide exhibited one melting peak at 84.5 °C, and methylcellulose indicated one exothermic event. Nevertheless, acrylamide was considered more stable than methylcellulose. The TG curves of the hydrogels exhibited three mass loss events, and on the DSC curves, three endothermic events were observed. It was verified that the different acrylamide proportions influenced the thermic behavior of hydrogels, and that the authors considered the 7.2% hydrogel a promising drug carrier system. The absorption bands were well defined, confirming the presence of the functional groups in the samples.     

Separation and determination of <Superscript>90</Superscript>Sr in low- and intermediate-level radioactive wastes using extraction chromatography and LSC

A methodology for the determination of ⁹⁰Sr in low- and intermediate-level radioactive wastes from nuclear power plants is presented in this work. It is a part of a methodology developed for the sequential radiochemical separation of radionuclides difficult-to-measure directly by gamma spectrometry in these radioactive wastes. The separation procedure was carried out using precipitation and extraction chromatography with Sr Resin, from Eichrom and the ⁹⁰Sr was measured by liquid scintillation counting (LSC). Optimum conditions for the pretreatment, separation and LSC measurements were determined using simulated samples, which were prepared using standard solutions and carriers. The procedure showed to be rapid and achieved a good chemical yield, in the range 60–90%, and a detection limit of 6.0 × 10⁻⁴ Bq g⁻¹. The method was also tested by participation in a national intercomparison program, with aqueous samples, with good agreement of results.     

Catalytic effect of lucunary heteropolyanion containing molybdenum and tungsten atoms on decolorization of direct blue 71

In this research,a lucunary Keggin structure,[PMo₂W₉O₃₉]^7- was selected as an efficient homogenous catalyst for degradation of an azo dye（direct blue 71） and a simple method was developed for degradation of DB71.The method is based on the oxidation of azo dye in the presence of a lucunary Keggin form of polyoxometalates,K₇[PMo₂W₉O₃₉]? 19H₂O,as a homogenous catalyst at room temperature.The reaction is monitored spectrophotometrically by measuring the absorbance of dye atλ=585 nm.Some parameters including concentration of catalyst,concentration of H₂O₂,pH and reaction time were investigated and optimized. Results show that K₇[PMo₂W₉O₃₉]? 19H₂O is more efficient in the presence of hydrogen peroxide.Degradation of dye in the presence of the catalyst and H₂O₂ could lead to the disappearance approximately 65%of dye after 60 min.But degradation for the same experiment performed in the absence of catalyst or in the absence of H₂O₂ was 22%or 5%respectively.Approximately 87% azo dyes has been eliminated after 90 min in the presence of catalyst,H₂O₂ and optimize conditions(0.6 g/L of K₇[PMo_2- W₉O₃₉H₉H₂O,0.08 mol/L hydrogen peroxide and room temperature).     

Synthesis and characterization of new porphyrin/4-quinolone conjugates

New porphyrin/4-quinolone conjugates were synthesized from the Suzuki-Miyaura coupling reaction of a β-borylated porphyrin with bromo-4-quinolones containing N-ethyl and N-d-ribofuranosyl substituents. The use of electrospray ionization tandem mass spectrometry showed important information about the fragmentation pathways of the new compounds. It was possible to distinguish between those compounds with the porphyrin moiety linked at the 6-position of the quinolone unit from their 7-substituted isomers. The new compounds showed to be good singlet oxygen generators.     

Structural flexibility and role of vicinal 2-thienyl rings in 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], its palladium(II) complex [(CN)2Th2Pyz(PdCl2)2], and the related pentametallic pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = Mg(II)(H2O), Zn(II))

The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)(2)Th(2)Pyz], and its Pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C(6)H(5)CN)(2)PdCl(2)] were characterized by X-ray, UV-visible, (1)H and (13)C NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd(II) coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, with identical Pd-N(pyz) (2.03(3) ?) and Pd-Cl (2.36(3) ?) bond lengths but with different Pd-S1 (2.25(4) ?) and Pd-S2 (3.21(5) ?) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd(II) derivative. (1)H/(13)C NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl(2) with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg(II)(H(2)O) or Zn(II). Spectroscopic data on the newly synthesized [(PdCl(2))(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl(2) involves coordination sites of the type S(2(th))PdCl(2) with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd(II) in an equivalent manner ("th-th" coordination). This is similar to what was found for the corresponding octapyridinated analogues ("py-py" coordination).     

Synthetic transformations of higher terpenoids: XXV. Cross coupling of phlomisoic acid methyl ester with alkenes in the presence of oxidants

The reaction of phlomisoic acid methyl ester with styrene, catalyzed by Pd(OAc)₂, in the presence of Cu(OAc)₂ and 1,4-benzoquinone in a mixture of propionic acid with diethyl ether gave the corresponding 15,16-distyryl derivative and only traces of 15- and 16-monosubstituted furanolabdanoids. Oxidative coupling of the title compound with methyl acrylate under analogous conditions afforded a mixture of 15-mono-, 16-mono-, and 15,16-dialkenylation products whose ratio changed during the process. The reaction was stereoselective, and the exocyclic double bond in the products had exclusively E configuration.     

N-Trifluoroacetyl-3a,4,5,9b-tetrahydro-3H-cyclopenta[c]quinoline ozonides

A three-component condensation of aromatic amine, aldehyde, and cyclopentadiene with subsequent N-trifluoroacetylation leads to 4- and 4,8-substituted N-trifluoroacetyl-3a,4,5,9b-tetrahydro-3H-cyclopenta[c]quinolines. Ozonation of the double bond in the latter produced the corresponding isomeric stable ozonides having (1R*,4S*,5aR*,6S*,11bR*)-configuration and differing in inversion at the carboxamide nitrogen atom.     

The structure of electron beam-modified cellulose triacetate

The structure, relaxation, and surface properties of cellulose triacetate (CTA) fibers and films modified by electron-beam irradiation in the absorbed dose range of D = 0−1000 kGy have been studied. The relation of the glass transition and melting temperatures of the irradiated CTA samples with the local density and the fractal dimensionality of the macrochain has been revealed. It has been shown that the radiation-chemical processes associated with the rupture of acetal bonds and the hydrolysis of CTA acetate groups predetermine the change in the structural and relaxation characteristics of the irradiated samples, as well as a nonmonotonic form of the dependence of the density and the surface energy of the films upon the absorbed dose near the threshold value of D = 75 kGy.     

Unusual crystal and molecular structure of the 1-(1-silatranylmethyl)-3,5-dimethylpyrazole complex with zinc dichloride

The crystal and molecular structure of a 1-(1-silatranylmethyl)-3,5-dimethylpyrazole complex with zinc dichloride (I) is determined by XRD. The coordination polyhedron of the zinc atom is a tetrahedron formed by two covalent Zn-Cl bonds and coordination Zn ← N and Zn ← O bonds. Compound I is the first example of how an endocyclic oxygen atom of the silatranyl fragment participates in the coordination of the metal atom with the formation of a six-membered heterocycle.