An evaluation by density functional theory of M-M interactions in organometallic clusters with the [Fe(3)MoS(3)](2+) cores

Density functional theory calculations were carried out on the structurally characterized [(Cl(4)-cat)Mo(py)Fe(3)S(3) (CO)(4)(P(n)Pr(3))(3)], A, and (Cl(4)-cat)Mo(py)Fe(3)S(3)(CO)(6)(PEt(3))(2), B, and also on A(2)(-) and B(2+) clusters. The Fe-Fe distances in these molecules depend on the total number of valence electrons (60 e(-) in A and B(2)(+) and 62 e(-) in A(2)(-) and B) and undergo great structural changes upon addition or removal of electrons. The changes are consistent with known electron-counting rules in organometallic chemistry. The weak nature of the Fe-Fe bonding interactions in these clusters is apparent in the very similar energies of states with widely different Fe-Fe distances.     

Functional polymers and sequential copolymers by phase transfer catalysis. 18. Synthesis and characterization of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) and α,ω-bis(vinylbenzyl)–poly(2,6-dimethyl-1,4-phenylene oxide) oligomers

A novel and convenient synthetic method for the preparation of α,ω-bis(2,6-dimethylphenol)–poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-2OH) is presented. It is based on the oxidative copolymerization of 2,6-dimethylphenol (DMP) with 2,2′-di(4-hydroxy-3,5-dimethylphenyl propane) (TMBPA) in a mixture of water–methanol or chlorobenzene–methanol. By using a 4/1 mole ratio of DMP to TMBPA and different solvent mixtures, it was possible to obtain bifunctional PPO-2OHs with number average molecular weights between 1000 and 5000. A phase-transfer-catalyzed etherification of PPO-2OH chain ends with a mixture of m- and p-chloromethylstyrene was used to synthesize α,ω-bis(vinylbenzyl)-poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO-2VBs). The thermal polymerization of the PPO-2VBs was studied by differential scanning calorimetry, and has demonstrated a very high thermal reactivity for this new class of reactive oligomers.     

Cantilever Functionalization Using Peroxidase Extract of Low Cost for Glyphosate Detection

A highly efficient process for reducing the fatty acid (FA) content of high-acid rice bran oil (RBO) was developed by immobilized partial glycerides-selective lipase SMG1-F278N-catalyzed esterification/transesterification using methanol as a novel acyl acceptor. Molecular docking simulation indicated that methanol was much closer to the catalytic serine (Ser-171) compared with ethanol and glycerol, which might be one of the reasons for its high efficiency in the deacidification of high-acid RBO. Additionally, the reaction parameters were optimized to minimize the FA content of high-acid RBO. Under the optimal conditions (substrate molar ratio of methanol to FAs of 1.8:1, enzyme loading of 40 U/g, and at 30 °C), FA content decreased from 25.14 to 0.03% after 6 h of reaction. Immobilized SMG1-F278N exhibited excellent methanol tolerance and retained almost 100% of its initial activity after being used for ten batches. After purification by molecular distillation, the final product contained 97.86% triacylglycerol, 2.10% diacylglycerol, and 0.04% FA. The acid value of the final product was 0.09 mg KOH/g, which reached the grade one standard of edible oil. Overall, methanol was a superior acyl acceptor for the deacidification of high-acid RBO and the high reusability of immobilized SMG1-F278N indicates an economically attractive process.     

Proficiency tests to evaluate commercially available IVD kits for glucose and cholesterol measurements

The first proficiency testing round 630-IL-1002, was carried out with a Reference Material DMR-180a with reference values obtained by using gas chromatography isotope dilution mass spectrometry methods, in which glucose, cholesterol and creatinine were measured. The serum pool was obtained from blood donors and all the analytes were at the normal concentration in Mexican population. The laboratories participants used different field methods to measure the analytes. The Mexican compulsory standard NOM-064-SSA1-1993 “specifications for equipments in vitro diagnostic (IVD)” requests 5% precision and 5% maximum bias of the IVD equipments in the measurements of analytes like glucose and cholesterol. The results obtained by field laboratories in the proficiency testing round are compared to the reference value and uncertainty provided by the National Metrology Institute (CENAM). The quality of measurements is dependent not only on the laboratory competence but also on the methods used by those commercially available IVD kits. It is concluded that quality assessment of measurements in clinical laboratories should be critically evaluated by using stable and certified reference materials. Presented at MEFNM 2008, September 2008, Budapest, Hungary.     

Effect of the Support on the Structural Characteristics of Tin

Tin oxide was supported on alumina, titania, magnesia and silica, treated with hydrogen at different temperatures and characterized by Mössbauer spectroscopy and X-ray diffraction. For the samples calcined at 773 K, tin is present as SnO₂ on alumina, magnesia and silica, but it occupies Ti sites on titania. After hydrogen treatment at high temperatures, tin is reduced from Sn(IV) to Sn(II) on alumina and titania, from Sn(IV) to Sn(0) on silica, but practically not reduced on magnesia. These results show the different degree of interaction between tin and the supporting material.     

The role of carbon and metal in self-assembly of the iron-carbon system at various component ratios

The problem of self-assembly in a metal-carbon system under dynamic conditions (equilibrium and nonequilibrium) is considered using the iron-carbon system as an example. It is proved theoretically and experimentally that the ratio of the components of the system affects the possibility of carbon self-assembly with the formation of fractal iron structures and of metal self-assembly with the participation of polyhapto derivatives of iron and the formation of fullerene-like carbon structures.     

Tin-Platinum catalysts interactions on titania and silica

Pt-Sn was supported on titania and silica, and the resulting interactions between the components in prepared samples and the resulting interactions between the components before and after treatment with hydrogen were characterized by Mössbauer spectroscopy, X-ray diffraction, Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and catalytic tests data. Results show the presence of Pt and SnO₂ after calcinations, and Pt₃Sn, PtSn and PtSn₃ after reduction. Rietveld analysis shows that some Ti⁴⁺ are replaced by Sn⁴⁺ atoms in the titania structure. Finally, HRTEM and the practically absence of activity observed confirms that metallic platinum is encapsulated.     

Synthesis of aromatic polyethers by Scholl reaction. I. Poly(1,1′-dinaphthyl ether phenyl sulfone)s and poly(1,1′-dinaphthyl ether phenyl ketone)s

A novel synthetic method for the preparation of high molecular weight aromatic polyethers is presented. It consists in the Scholl reaction of di(1-naphthyl) ethers of aromatic derivatives exhibiting lower nucleophilicity and higher oxidation potential than the 1-naphthoxy groups. The examples described in this paper refer to the synthesis of aromatic polyether sulfones and aromatic polyether ketones by the polymerization of 4,4′-di(1-naphthoxy)diphenyl sulfone and respectively 4,4′-di(1-naphthoxy)benzophenone. Both polymerization reactions are performed at room temperature in nitrobenzene, using anhydrous FeCl₃ as catalyst, and apparently follow a “reactive intermediate polycondensation” polymerization mechanism.