Stereoselective synthesis of (+)-polyoxamic acid based on the synthesis of chiral oxazine

A concise, stereocontrolled synthesis of (+)-polyoxamic acid was achieved. Starting from trans-oxazoline as a chiral building block, the key step involves diastereoselective oxazine formation catalyzed by palladium(0).     

Chiral phosphoramide-catalyzed aldol additions of ketone trichlorosilyl enolates. Mechanistic aspects

The mechanism of the catalytic, enantioselective addition of trichlorosilyl enolates to aldehydes has been investigated. Kinetic studies using ReactIR and rapid injection NMR (RINMR) spectroscopy have confirmed the simultaneous operation of dual mechanistic pathways involving either one or two phosphoramides bound to a siliconium ion organizational center. This mechanistic dichotomy was initially postulated on the basis of catalyst loading studies and nonlinear effects studies. This duality explains the difference in reactivity and stereoselectivity of various classes of phosphoramides. Determination of Arrhenius activation parameters revealed that aldol addition occurs through the reversible albeit unfavorable formation of an activated complex, and natural-abundance 13C NMR kinetic isotope effect (KIE) studies have determined that the turnover limiting step is the aldol addition. A thorough examination of a range of phosphoramides has established empirical structure-activity selectivity relationships. In addition, the effects of catalyst loading, rate of addition, solvents, and additives have been studied and together allow the formulation of a unified mechanistic picture for the aldol addition.     

Functional organotrimethoxysilane derivative with strong intermolecular pi-pi interaction: one-pot grafting reaction on oxidized silicon substrates

Although the fabrication of self-assembled monolayers (SAMs) on an oxidized silicon substrate with special functionality is an important topic for various applications, it is still very difficult to obtain a densely grafted monolayer. With a newly synthesized organotrimethoxysilane containing a 1-cyano-1,2-bisbiphenyl-ethylene (CNMBE) moiety which provides a strong pi-pi intermolecular interaction, an SAM of well-ordered structure is readily obtained by a one-pot grafting reaction under mild conditions. The aggregation process of the CNMBE moiety, which induced a close packing of organosilane on the substrate, was visually monitored by the fluorescence of the monolayer grafted on quartz.     

Z \to b\bar b in a composite model of fermions

A composite model of fermions is proposed to explain the “anomaly” in $Z \to b\bar b$ and, to a lesser extent, in $Z \to c\bar c$ It contains a nonsequential fourth family whose mass of one member (the charge ? 1/3 quark) is constrained to be between 47 GeV and 49 GeV. The charge + 2/3 quark is constrained to lie between 67 GeV and 107 GeV. This opens up the exciting prospect for nearfuture discoveries at LEP2 and possibly at the Tevatron.     

"Simulating synthesis": ceria nanosphere self-assembly into nanorods and framework architectures

We predict, from computer modeling and simulation in partnership with experiment, a general strategy for synthesizing spherical oxide nanocrystals via crystallization from melt. In particular we "simulate synthesis" to generate full atomistic models of undoped and Ti-doped CeO2 nanoparticles, nanorods, and nanoporous framework architectures. Our simulations demonstrate, in quantitative agreement with experiment [Science 2006, 312, 1504], that Ti (dopant) ions change the shape of CeO2 nanocrystals from polyhedral to spherical. We rationalize this morphological change by elucidating, at the atomistic level, the mechanism underpinning its synthesis. In particular, CeO2 nanocrystals can be synthesized via crystallization from melt: as a molten (undoped) CeO2 nanoparticle is cooled, nucleating seeds spontaneously evolve at the surface and express energetically stable [111] facets to minimize the energy. As crystallization proceeds, the [111] facets grow, thus facilitating a polyhedral shape. Conversely, when doped with Ti, a (predominantly) TiO2 shell encapsulates the inner CeO2 core. This shell inhibits the evolution of nucleating seeds at the surface thus rendering it amorphous during cooling. Accordingly, crystallization is forced to proceed via the evolution of a nucleating seed in the bulk CeO2 region of the nanoparticle, and as this seed grows, it remains surrounded by amorphous ions, which "wrap" around the core so that the energies for high-index facets are drastically reduced; these amorphous ions adopt a spherical shape to minimize the surface energy. Crystallization emanates radially from the nucleating seed, and because it is encapsulated by an amorphous shell, the crystallization front is not compelled to express energetically favorable surfaces. Accordingly, after the nanoparticle has crystallized it retains this spherical shape. A typical animation showing the crystallization (with atomistic detail) is available as Supporting Information. From this data we predict that spherical oxide nanocrystals can be synthesized via crystallization from melt in general by suppressing nucleating seed evolution at the surface thus forcing the nucleating seed to spontaneously evolve in the bulk. Nanospheres can, similar to zeolitic classifications, constitute Secondary Building Units (SBUs) and can aggregate to form nanorods and nanoporous framework architectures. Here we have attempted to simulate this process to generate models for CeO2 and Ti-doped CeO2 nanorods and framework architectures. In particular, we predict that Ti doping will "smooth" the surfaces: hexagonal prism shaped CeO2 nanorods with [111] and [100] surfaces become cylindrical, and framework architectures change from facetted pores and channels with well-defined [111] and [100] surfaces to "smooth" pores and channels (expressing both concave and convex curvatures). Such structures are difficult to characterize using, for example, Miller indices; rather we suggest that these new structural materials may be better described using minimal surfaces.     

Cryopreservation of garlic bulbil primordia by the droplet-vitrification procedure

The droplet-vitrification protocol, a combination of droplet-freezing and solution-based vitrification was applied for cryopreserving garlic bulbil primordia. The highest survival and regeneration percentages of cryopreserved primordia (90.1 to 95.0 percent and 82.7 to 85.0 percent, respectively) were achieved after preculture for 2-4 days at 10 degree C on solid medium with 0.1 - 0.3 M sucrose, loading for 50 minutes in liquid medium with 2 M glycerol + 0.5 M sucrose, dehydration with PVS3 vitrification solution for 90-150 min, cooling primordia in 5 microl droplets of PVS3 vitrification solution placed on aluminum foil strips by dipping these strips in liquid nitrogen, warming them by plunging the foil strips into pre-heated (40 degree C) 0.8 M sucrose solution for 30 s and further incubation in the same solution for 30 minutes. The optimized droplet-vitrification protocol was successfully applied to bulbil primordia of five garlic varieties originating from various countries and to immature bulbils of two vegetatively propagated Allium species, with regeneration percentages ranging between 77.4 - 95.4 percent.     

Selectivity and sensitivity of a reagentless electrochemical DNA sensor studied by square wave voltammetry and fluorescence

Poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic acid-1,4-naphthoquinone)-modified electrode is used for the direct electrochemical detection of oligonucleotide hybridization. The polymer film presents well-defined electroactivity in the cathodic potential domain (between 0 and -0.8 V/SCE), due to the quinone group embedded into the polymer structure. The detection can be performed simply by square wave voltammetry. This sensor is a "signal-on" device and works with different oligonucleotide lengths, from 10 to 30 bases. Quantitative results from fluorescence are consistent with electrochemical data. It is confirmed that the signal increase in square wave voltammetry is unambiguously due to hybridization. The biosensor presents a detection limit of target of ca. 25 nM and is highly selective as it can discriminate single mismatch base.     

A reversible polymorphic phase change which affects the luminescence and aurophilic interactions in the gold (I) cluster complex, [mu3-S(AuCNC7H13)3](SbF6)

Crystallographic examination of [mu3-S(AuCNC7H13)3](SbF6) shows that it undergoes a reversible phase change from orthorhombic to monoclinic upon cooling. At 190 K, the structure shows that two cations self-associate to form a pseudo-octahedral array of six gold atoms connected by both intra- and interionic aurophilic interactions. On cooling, the clusters become less symmetric, and in one, the interionic Au...Au separations increase, while they decrease in the second cluster. The luminescence of crystalline [mu3-S(AuCNC7H13)3](SbF6) shows corresponding changes in emission, with two emissions of similar lifetimes but with different excitations at 77 K, but only a single emission at 298 K. In contrast, [mu3-S(AuCNC6H11)3](PF6), which has a similar structure to that of the high-temperature form of [mu3-S(AuCNC7H13)3](SbF6), does not undergo a phase change or change in its luminescence upon cooling.