Real-time analysis of methylalumoxane formation

Methylalumoxane (MAO), a perennially useful activator for olefin polymerization precatalysts, is famously intractable to structural elucidation, consisting as it does of a complex mixture of oligomers generated from hydrolysis of pyrophoric trimethylaluminum (TMA). Electrospray ionization mass spectrometry (ESI-MS) is capable of studying those oligomers that become charged during the activation process. We have exploited that ability to probe the synthesis of MAO in real time, starting less than a minute after the mixing of H₂O and TMA and tracking the first half hour of reactivity. We find that the process does not involve an incremental build-up of oligomers; instead, oligomerization to species containing 12–15 aluminum atoms happens within a minute, with slower aggregation to higher molecular weight ions. The principal activated product of the benchtop synthesis is the same as that observed in industrial samples, namely [(MeAlO)₁₆(Me₃Al)₆Me]⁻, and we have computationally located a new sheet structure for this ion 94 kJ mol⁻¹ lower in Gibbs free energy than any previously calculated.

The activator methylaluminoxane is made by hydrolysis of trimethylaluminum. Analysis using ESI-MS reveals rapid formation of small oligomers is followed by slower aggregation to the larger precursors most capable of releasing [Me₂Al]⁺.     

Hydrolysis and Desulfurization of the Diastereomeric Phosphoromonothioate Analogs of Uridine 2',3'-Cyclic Monophosphate

Hydrolyses of the two diastereomeric phosphoromonothioate analogs of uridine 2',3'-cyclic monophosphate [(R(P))- and (S(P))-2',3'-cUMPS] at 363.2 K have been followed by HPLC over pH-range 0-12. In aqueous alkali (pH > 9) only base-catalyzed endocyclic phosphoester hydrolysis to a nearly equimolar mixture of uridine 2'- and 3'-phosphoromonothioates (2'- and 3'-UMPS) takes place, analogously to the hydrolysis of uridine 2',3'-cyclic monophosphate (2',3'-cUMP). The (R(P))- and (S(P))-2',3'-cUMPS are hydrolyzed 50 and 30%, respectively, more slowly than 2',3'-cUMP. Under neutral and acidic conditions, desulfurization of the cyclic thiophosphates to 2',3'-cUMP competes with the phophoester hydrolysis, both reactions being acid-catalyzed at pH < 5. The desulfurization is most pronounced in strongly acidic solutions ([HCl] > 0.1 mol L(-)(1)), where more than 90% of the starting material is degraded via this route. At pH < 2, the thioates are considerably, i.e., more than 1 order of magnitude, more stable than 2',3'-cUMP. While the hydrolysis of 2',3'-cUMP is second-order in hydronium-ion concentration, that of 2',3'-cUMPS exhibits a first-order dependence. The reactivities of the two diastereomers are comparable with each other over the entire pH-range studied, the most significant difference being that the pH-independent desulfurization at pH > 5 is with the R(P)-isomer 5-fold faster than with the S(P)-isomer. In contrast to 2',3'-cUMP, depyrimidination of the starting material (i.e., release of the uracil base) competes with the hydrolysis of the thiophosphate moiety under neutral conditions (pH 6-8).     

Impact of cholesterol on voids in phospholipid membranes

Free volume pockets or voids are important to many biological processes in cell membranes. Free volume fluctuations are a prerequisite for diffusion of lipids and other macromolecules in lipid bilayers. Permeation of small solutes across a membrane, as well as diffusion of solutes in the membrane interior are further examples of phenomena where voids and their properties play a central role. Cholesterol has been suggested to change the structure and function of membranes by altering their free volume properties. We study the effect of cholesterol on the properties of voids in dipalmitoylphosphatidylcholine (DPPC) bilayers by means of atomistic molecular dynamics simulations. We find that an increasing cholesterol concentration reduces the total amount of free volume in a bilayer. The effect of cholesterol on individual voids is most prominent in the region where the steroid ring structures of cholesterol molecules are located. Here a growing cholesterol content reduces the number of voids, completely removing voids of the size of a cholesterol molecule. The voids also become more elongated. The broad orientational distribution of voids observed in pure DPPC is, with a 30% molar concentration of cholesterol, replaced by a distribution where orientation along the bilayer normal is favored. Our results suggest that instead of being uniformly distributed to the whole bilayer, these effects are localized to the close vicinity of cholesterol molecules.     

Icosahedral and ring-shaped allotropes of arsenic.

We predict the existence of two novel families of arsenic nanostructures: icosahedral cages and ring-shaped chains. Quantum chemical calculations on the cages, rings, and the experimentally known allotropes of arsenic suggest the nanostructures to be thermodynamically stable. The icosahedral cages are modifications of the gray allotrope of arsenic, while the ring-shaped chains are structurally related to the red allotrope of phosphorus. Comparisons between the analogous allotropes of arsenic and phosphorus show distinct differences. While phosphorus favors the ring-shaped chains over the icosahedral cages, large cages become favorable for arsenic. From the thermodynamical point of view, experimental preparation of the proposed families of arsenic nanostructures is expected to be viable.     

Executive views concerning decision support tools

Support tools for strategic-level decision-making have become increasingly popular. This study investigates the role of OR/MS tools in today’s strategic-level decision support tool market. Executives working in Finland’s 500 largest companies were asked about the decision support tools they use when making major decisions. The responses received indicated that executives actively use a variety of tools, and an average of five different strategic-level tools. Approximately 10% of the tools used could be identified as OR/MS type, these often suit the needs of larger companies with strategic logistical or production functions and compared to other tools, have a specific profile. Executives see advantages in using tools that provide cognitive, collaboration and communication possibilities, and also in using tools that make processes more efficient. OR methodologies have influenced some of the other tools on the market, but ‘soft OR’ tool usage could not be identified. Tools which support creativity are needed.     

Grafting of montmorillonite nano‐clay with butyl acrylate and methyl methacrylate by atom transfer radical polymerization: Blends with poly(BuA‐co‐MMA)

11‐(2‐Bromo‐2‐methyl)propionyl‐oxy‐undecyl trichlorosilane atom transfer radical polymerization (ATRP) initiator was covalently attached on montmorillonite clay platelets via silylation reactions. The initiator clay was used to polymerize butyl acrylate (BuA) and methyl methacrylate (MMA) on the clay surface. Polymerization was performed in bulk monomer solution or in DMSO. Polymer modified clay was mixed with a poly(BuA‐co‐MMA) matrix. Small angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM) showed that clay modified in DMSO gave exfoliated composites when mixed with the matrix copolymer. Mechanical properties of the composites were studied by dynamic mechanical thermal analysis (DMTA). The results showed that the mechanical properties were improved as a function of clay content, as well with an increasing homogeneity of the nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3086–3097, 2009     

Sorption of silicic acid from non-saturated aqueous solution by a complex of zinc ions with poly(vinylamine)

Silicifying organisms (diatom algae, sponges, etc.) build multifarious silica and composite nano-structures which attracts rapt attention of specialists in nanotechnology. These organisms can capture monomeric silicic acid from diluted solutions (<1 mM) and molecular mechanism of this process is still unknown. Some hypotheses include mediatorial role of zinc ions coordinated with a special protein transporter. We have studied several basic hydrogels and their complexes with double charged metal ions in sorption of silicic acid from non-saturated solutions. Cross-linked poly(vinylamine) coordinated with Zn²⁺ was able to capture silicic acid from 0.1 to 1.7 mM solutions. The other ions (Cu²⁺, Fe²⁺, Ni²⁺, Co²⁺, Cd²⁺ and Mn²⁺) and less basic poly(1-vinylimiazole) were not active in the sorption. A mechanism included oligomerization of silicic acid and formation of triple complex poly(vinylamine)-Zn²⁺-oligosiloxane was proposed. FTIR, NMR and EDS data confirm this conclusion. The found capture of silicic acid from diluted solutions with polyamine-zinc complex shows possibility in principle of the zinc-mediated transmembrane transport of Si(OH)₄ in silicifying organisms. On the other hand, the ability of zinc ions immobilized on the polyamine support to capture oligosilicates could be used in directed assembly of nanocomposite structures by the “bottom-up” approaches.     

Assessment of interstitial water content of articular cartilage with T1 relaxation

The interstitial water content typically increases in the early degeneration of articular cartilage. Previously, T₂ relaxation has been related to water content, yet it is known to be strongly affected by the collagen orientation. Articular cartilage plugs from the bovine patella, femur and tibia (N=20) were mapped for T₁ and T₂ at 9.4 T to test the ability of T₁ relaxation to reflect cartilage water content. As a reference, water and proteoglycan (PG) contents were determined. Significant (P<.01) linear associations were demonstrated between the relaxation rates and tissue water content (R₁: r=−.81, R₂: r=−.60) and PG content (R₁: r=.75). After adjustment for the tissue water content, partial correlation analysis did not show significant associations between the relaxation rates and tissue PG content. After the effect of PGs was removed, significant (P<.05) linear correlation between the relaxation rates and tissue water content (R₁: r=−.48, R₂: r=−.50) was observed. Thus, the spin-lattice relaxation rate is proposed to provide a biomarker for water content in articular cartilage.     

Methods of artificial enlargement of the training set for statistical shape models

Due to the small size of training sets, statistical shape models often over-constrain the deformation in medical image segmentation. Hence, artificial enlargement of the training set has been proposed as a solution for the problem to increase the flexibility of the models. In this paper, different methods were evaluated to artificially enlarge a training set. Furthermore, the objectives were to study the effects of the size of the training set, to estimate the optimal number of deformation modes, to study the effects of different error sources, and to compare different deformation methods. The study was performed for a cardiac shape model consisting of ventricles, atria, and epicardium, and built from magnetic resonance (MR) volume images of 25 subjects. Both shape modeling and image segmentation accuracies were studied. The objectives were reached by utilizing different training sets and datasets, and two deformation methods. The evaluation proved that artificial enlargement of the training set improves both the modeling and segmentation accuracy. All but one enlargement techniques gave statistically significantly $(p ≪ 0.05)$ better segmentation results than the standard method without enlargement. The two best enlargement techniques were the nonrigid movement technique and the technique that combines principal component analysis (PCA) and finite element model (FEM). The optimal number of deformation modes was found to be near 100 modes in our application. The active shape model segmentation gave better segmentation accuracy than the one based on the simulated annealing optimization of the model weights.