A case of concomitant polymorphism and spontaneous resolution: the tetragonal phase of 5‐hydroxymethyl‐7,7,N‐trimethyl‐6‐oxabicyclo[3.2.1]octane‐1‐carboxamide

The title compound, C₁₂H₂₁NO₃, crystallizes in two polymorphic forms, viz. the tetragonal form described here and the monoclinic form described previously [Foces‐Foces, López‐Rodríguez, Pérez, Martín & Pérez‐Hernández (2007). Cryst. Growth Des. 7 , 905–911]. The differences in the conformations of the hydroxymethyl and methylaminocarbonyl substituents have important consequences in the hydrogen‐bond interaction motifs and, therefore, in the packing arrangements. These forms are concomitant polymorphs with melting points differing by 3 K.     

Effect of excess halide on the palladium‐catalyzed insertion‐triggered radical copolymerization of methyl acrylate and 1‐hexene

[Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) is a very efficient initiator of the radical polymerization of methyl acrylate, but it is not active in the polymerization of methyl methacrylate or in the copolymerization with 1‐hexene. The addition of an excess of NBu₄Cl to solutions of [Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) provides an initiator system that copolymerizes methyl acrylate and 1‐hexene by an insertion‐triggered radical mechanism. Random copolymers are obtained with 11% incorporation of 1‐hexene in moderate yields (about 35%). Studies of the decomposition products obtained after the first insertion of methyl acrylate in the Pd? C₆F₅ bond of 1 show that the addition of excess halide in the presence of monomer favors the homolytic cleavage of the Pd? C bond, and the generation of the radicals that are active species in the polymerization, versus alternative evolution pathways. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5682–5691, 2006     

Metallocene copolymers of propene and 1‐hexene: The influence of the comonomer content and thermal history on the structure and mechanical properties

The relationships between the structure and properties have been established for copolymers of propylene and 1‐hexene synthesized with an isotactic metallocene catalyst system. The most important factor affecting the structure and properties of these copolymers is the comonomer content. The thermal treatment, that is, the rate of cooling from the melt, is also important. These factors affect the thermal properties, the degree of crystallinity, and therefore the structural parameters and the viscoelastic behavior. A slow cooling from the melt favors the formation of the γ phase instead of the α modification. Regarding the viscoelastic behavior, the β relaxation, associated with the glass‐transition temperature, is shifted to lower temperatures and its intensity is increased as the 1‐hexene content raises. The microhardness values are correlated with those of the storage modulus deduced from dynamic mechanical thermal analysis curves, and good linear relations have been obtained between these parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1253–1267, 2006     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Determination of lithium in human serum by electrothermal atomic absorption spectrometry

An efficient method was developed for the determination of nanogram levels of lithium in biological samples. Serum samples from human subjects from southeastern Spain, treated or not treated with lithium carbonate, were analyzed by electrothermal atomic absorption spectrometry. The samples were previously treated with a matrix modifier consisting of 0.1% Triton X-100 and injected through a graphite tube with L'vov platform. The Li concentrations measured by the procedure described for the 3 certified reference samples used were not significantly different (p > 0.05) than certified levels. Sample recoveries and variability during several days, with coefficients of variation from 4.00 to 14.8%, demonstrated the reliability and accuracy of this technique. Mean Li concentration determined in the serum of individuals with psychiatric disorders treated with Li (n = 117, 5.077 +/- 1.795 microg Li/mL) was significantly higher (p < 0.001) than that in individuals not treated with Li (n = 24, 1.902 +/- 2.054 ng Li/mL).     

Synthesis and characterization of new di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes

Summary Several new neutral and cationic di- and tri-nuclear cyano-bridged bis(dioximato)cobalt(III) complexes have been synthesized and characterized (dioximato = dimethylglyoximato or diphenylglyoximato). These compounds are obtained through substitution of labile axial ligands by the nitrogen of the cyano-group in [Co(dioximato)₂(CN)₂]^– or [LCo(dioximato)₂(CN)] (L = H₂O, NH₃, or py). In the first case, the existence of only one band in the CN-stretching region of the i.r. spectrum at 2190–2200 cm^–1 is indicative of a trinuclear compound, while the presence of a second band at 2140 cm^–1 attributable to a terminal cyano-group indicates a dinuclear structure. In the presence of water, aquation of axial positions may take place at the same time as bridge formation, whereas the use of a non-aqueous solvent allows the preparation of complexes with pyridine or NH₃.     

Thermal rearrangements of 2-vinylcyclopropylidene to cyclopentadiene and vinylallene: a theoretical investigation

In an attempt to clarify the favored rearrangement reaction of vinylcyclopropylidenes, the prototype thermal rearrangements of singlet 2-vinylcyclopropylidene (1) leading to 1,3cyclopentadiene (2) and 1,2,4-pentatriene (vinylallene) (3) were investigated by means of ab initio quantum-mechanical electronic-structure calculations. The B3LYP functional with the 6-31G(d) basis set was employed for geometry optimization of the equilibrium and transition-state structures relevant to the two reaction pathways and for computing their harmonic vibrational frequencies. Final energies were evaluated by single-point calculations at the CCSD(T) level of theory with the 6-311 + G(3df,2p) basis set. The rearrangement of s-cis 1 to 2 is found to occur by a three-step pathway. The first step involves the formation of a nonclassical carbene (5), which is an internal pi complex between the pi molecular orbital of the double bond and the empty p atomic orbital of the carbene carbon. In the second step, the nonplanar five-membered ring geometry of 5 flattens to reach the planar structure of 3-cyclopentenylidene (4). The last step is the 1,2-migration of a alpha-hydrogen atom to the carbene center in 4. The rate-determining step for the rearrangement of s-cis 1 to 2 is the formation of 5, with a predicted global deltaG++(220 K) of only 0.6 kcalmol(-1). The rearrangement of s-trans 1 to 2 requires an initial conversion of s-trans 1 to the s-cis conformer, with a predicted deltaG++(220 K) of 1.8 kcalmol(-1). The transition structure for the ring-opening of s-trans 1 into s-trans 3 (deltaG++(220 K)=4.7 kcalmol(-1)) is more energetic than that for the ring-opening of s-cis 1 into s-cis 3 (deltaG++(220 K)=2.5 kcalmol(-2)) due to larger repulsive nonbonded H...H interactions in the former transition structure. On the basis of these results, it is suggested that if the reaction of 1,1-dibromo-2-vinylcyclopropane with methyllithium at -78 degrees C leads to the initial formation of carbene 1, then the reaction should yield 2 as the main product together with small amounts of 3. This theoretical prediction nicely agrees with experimental findings.     

A density functional theory study on the electrocyclization of 1,2,4,6-heptatetraene analogues: converting a pericyclic to a pseudopericyclic reaction

A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth.     

Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides

The effect of substituents on the reactivity and stereoselectivity of the SmI₂/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (α or β, respectively).     

RNA integrity as a quality indicator during the first steps of RNP purifications : A comparison of yeast lysis methods

Background  

The completion of several genome-sequencing projects has increased our need to assign functions to newly identified genes. The presence of a specific protein domain has been used as the determinant for suggesting a function for these new genes. In the case of proteins that are predicted to interact with mRNA, most RNAs bound by these proteins are still unknown. In yeast, several protocols for the identification of protein-protein interactions in high-throughput analyses have been developed during the last years leading to an increased understanding of cellular proteomics. If any of these protocols or similar approaches shall be used for the identification of mRNA-protein complexes, the integrity of mRNA is a critical factor.