Structure of the decamethyl titanocene cation,a metallocene with two agostic C-h bonds,and its interaction with fluorocarbons

The tetraphenylborate salt of the decamethyl titanocene cation, [Cp*2Ti][BPh4] (1, Cp* = C5Me5), was prepared by reaction of Cp*2TiH with [Cp2Fe][BPh4] and by reaction of Cp*2TiMe with [PhNMe2H][BPh4]. The crystal structure of 1 shows that the Cp*2Ti cation has a bent metallocene structure with agostic interactions with the metal center of two adjacent methyl groups on one of the Cp* ligands. Compound 1 reacts readily with THF to give the adduct [Cp*2Ti(THF)][BPh4] (2). In fluorobenzene, 1 forms the eta1-fluorobenzene adduct [Cp*2Ti(eta1-FC6H5)][BPh4] (3), which was structurally characterized. In contrast to the thermal stability of 3, addition of alpha,alpha,alpha-trifluorotoluene to either 1 or 2 results in C-F activation to give Cp*2TiF2 and PhCF2CF2Ph as the main products. This reactivity toward benzylic C-F bonds is also reflected in the reactivity toward the fluorinated borate anions [B(C6F5)4]- and {B(3,5-(CF3)2C6H3]4}-: reaction of Cp*2TiMe with their [PhNMe2H]+ salts results in a stable complex for the former anion, whereas rapid C-F activation is observed for the latter.     

Using magnetic levitation for 2D and 3D self‐assembly of cubic silicon macroparticles

Today's micro‐ and nano‐fabrication is essentially two‐dimensional, with very limited possibilities of accessing the third dimension. The most viable way to mass‐fabricate functional structures at the nano‐scale, such as electronics or MEMS, with equal feature sizes in all directions, is by three‐dimensional self‐assembly. Up to now, three‐dimensional self‐assembly has mainly been restricted to crystals of polymer spheres. We report on two‐ and three‐dimensional self‐assembly of silicon cubes, levitated in a paramagnetic fluid. We demonstrate the benefits of templating and study the effect of a change in hydrophilicity of the cubes. These experiments bring us one step closer to three‐dimensional self‐assembly of anisotropic, semiconducting units, which is a crucial milestone in overcoming the scaling limits imposed by contemporary 2D microfabrication.

     

Examining the Heterogeneous Genome Content of Multipartite Viruses BMV and CCMV by Native Mass Spectrometry

Since the concept was first introduced by Brian Chait and co-workers in 1991, mass spectrometry of proteins and protein complexes under non-denaturing conditions (native MS) has strongly developed, through parallel advances in instrumentation, sample preparation, and data analysis tools. However, the success rate of native MS analysis, particularly in heterogeneous mega-Dalton (MDa) protein complexes, still strongly depends on careful instrument modification. Here, we further explore these boundaries in native mass spectrometry, analyzing two related endogenous multipartite viruses: the Brome Mosaic Virus (BMV) and the Cowpea Chlorotic Mottle Virus (CCMV). Both CCMV and BMV are approximately 4.6 megadalton (MDa) in mass, of which approximately 1 MDA originates from the genomic content of the virion. Both viruses are produced as mixtures of three particles carrying different segments of the genome, varying by approximately 0.1 MDA in mass (~2%). This mixture of particles poses a challenging analytical problem for high-resolution native MS analysis, given the large mass scales involved. We attempt to unravel the particle heterogeneity using both Q-TOF and Orbitrap mass spectrometers extensively modified for analysis of very large assemblies. We show that manipulation of the charging behavior can provide assistance in assigning the correct charge states. Despite their challenging size and heterogeneity, we obtained native mass spectra with resolved series of charge states for both BMV and CCMV, demonstrating that native MS of endogenous multipartite virions is feasible.

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Formation of enantiopure 5-substituted oxazolidinones through enzyme-catalysed kinetic resolution of epoxides

Halohydrin dehalogenase from Agrobacterium radiobacter catalyzed the enantioselective ring opening of terminal epoxides with cyanate as a nucleophile, yielding 5-substituted oxazolidinones in high yields and with high enantiopurity (69-98% ee). This is the first example of the biocatalytic conversion of a range of epoxides to the corresponding oxazolidinones.     

MHz unidirectional rotation of molecular rotary motors

A combination of cryogenic UV-vis and CD spectroscopy and transient absorption spectroscopy at ambient temperature is used to study a new class of unidirectional rotary molecular motors. Stabilization of unstable intermediates is achieved below 95 K in propane solution for the structure with the fastest rotation rate, and below this temperature measurements on the rate limiting step in the rotation cycle can be performed to obtain activation parameters. The results are compared to measurements at ambient temperature using transient absorption spectroscopy, which show that behavior of these motors is similar over the full temperature range investigated, thereby allowing a maximum rotation rate of 3 MHz at room temperature under suitable irradiation conditions.     

Novel Surface Modification of Sulfur by Plasma Polymerization and its Application in Dissimilar Rubber-Rubber Blends

In this study, surface modification of elemental sulfur by plasma polymerization with acetylene, perfluorohexane and acrylic acid is described, with the aim of changing the surface properties of sulfur without losing the bulk properties and reactivities in the vulcanization process. Significant improvements are obtained in dissimilar elastomer blends using the encapsulated sulfur powders. The conditions for the plasma polymerization were varied in order to obtain the optimal performance of the modified sulfur. The imperfections in the shell structure, obtained with plasma polymers, act as gateways to release sulfur for the vulcanization reaction.     

Reversible three-state switching of luminescence: a new twist to electro- and photochromic behavior

The fully reversible three-state blue/red/off emission from photo-/electrochromic substituted bis-thiaxanthylidenes is reported. The blue luminescence of the most stable (anti-folded) conformer of dimethyl- and dimethoxy-bis-thiaxanthylidene can be switched off by photochemical conversion to the meta-stable (syn-folded) conformer and switched on again by thermal reversion to the anti-folded state. The red luminescence of the bis-thiaxanthylium dication can be switched on by oxidation at approximately 1.0 and 1.2 V vs SCE of the syn- and anti-folded conformers respectively and switched off or to blue by reduction at approximately 0.35 V vs SCE.     

End‐group modification of poly(butyl acrylate) prepared by atom transfer radical polymerization: Mechanistic study using gradient polymer elution chromatography

The introduction of a functional group into a poly(butyl acrylate) polymer prepared by copper‐mediated atom transfer radical polymerization and the characterization of the prepared polymer by gradient polymer elution chromatography are reported. The bromo end group of the initial polymer can be transformed into a different functional group with several functionalization reactions, including nucleophilic substitution and atom transfer radical addition (ATRA), in combination with comonomers, addition–fragmentation transfer agents, or stable radicals. Several new functionalization agents are reported, including ATRA using 1‐(3‐hydroxymethyl‐phenyl)‐pyrrole‐2,5‐dione and trimethyl{1‐[4‐(2‐trimethylsiloxyethoxy)]phenylethenyloxy}silane and nucleophilic substitution using 2‐mercapto ethanol. The rate constant of the functionalization reaction and the final functionality are determined with gradient polymer elution chromatography, a technique by which qualitative and quantitative information about the conversion can be obtained. Polymers with a functionality greater than 95% are reported. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2350–2359, 2002