Acyltransferase families that act on thioesters: Sequences, structures, and mechanisms.

Acyltransferases (AT) are enzymes that catalyze the transfer of acyl group to a receptor molecule. This review focuses on ATs that act on thioester-containing substrates. Although many ATs can recognize a wide variety of substrates, sequence similarity analysis allowed us to classify the ATs into fifteen distinct families. Each AT family is originated from enzymes experimentally characterized to have AT activity, classified according to sequence similarity, and confirmed with tertiary structure similarity for families that have crystallized structures available. All the sequences and structures of the AT families described here are present in the thioester-active enzyme (ThYme) database. The AT sequences and structures classified into families and available in the ThYme database could contribute to enlightening the understanding acyl transfer to thioester-containing substrates, most commonly coenzyme A, which occur in multiple metabolic pathways, mostly with fatty acids.

Self-assembly and orientation of hydrogen-bonded oligothiophene polymorphs at liquid-membrane-liquid interfaces.

One of the challenges in organic systems with semiconducting function is the achievement of molecular orientation over large scales. We report here on the use of self-assembly kinetics to control long-range orientation of a quarterthiophene derivative designed to combine intermolecular π-π stacking and hydrogen bonding among amide groups. Assembly of these molecules in the solution phase is prevented by the hydrogen-bond-accepting solvent tetrahydrofuran, whereas formation of H-aggregates is facilitated in toluene. Rapid evaporation of solvent in a solution of the quarterthiophene in a 2:1:1 mixture of 1,4-dioxane/tetrahydrofuran/toluene leads to self-assembly of kinetically trapped mats of bundled fibers. In great contrast, slow drying in a toluene atmosphere leads to the homogeneous nucleation and growth of ordered structures shaped as rhombohedra or hexagonal prisms depending on concentration. Furthermore, exceedingly slow delivery of toluene from a high molecular weight polymer solution into the system through a porous aluminum oxide membrane results in the growth of highly oriented hexagonal prisms perpendicular to the interface. The amide groups of the compound likely adsorb onto the polar aluminum oxide surface and direct the self-assembly pathway toward heterogeneous nucleation and growth to form hexagonal prisms. We propose that the oriented prismatic polymorph results from the synergy of surface interactions rooted in hydrogen bonding on the solid membrane and the slow kinetics of self-assembly. These observations demonstrate how self-assembly conditions can be used to guide the supramolecular energy landscape to generate vastly different structures. These fundamental principles allowed us to grow oriented prismatic assemblies on transparent indium-doped tin oxide electrodes, which are of interest in organic electronics.

Assembling p-type molecules on single wall carbon nanotubes for photovoltaic devices.

We report the design and synthesis of an oligothiophene molecule that noncovalently functionalizes carbon nanotubes to create a hybrid material for photovoltaic devices.

Chemical and physical properties of ultrafine diesel exhaust particles sampled downstream of a catalytic trap.

The chemical and physical properties of exhaust particles produced by a Caterpillar 3176 C-12 heavy duty diesel engine equipped with a catalytic trap (CRT) are reported. The engine was operated at 600 Nm and 1500 rpm, using fuels containing 15 and 49 ppm sulfur. A two-stage dilution tunnel designed to simulate the reactions that occur when hot combustion products mix with cooler atmospheric air was used. Particle size distributions were measured using a scanning mobility particle sizer (SMPS) and nano-scanning mobility particle sizer (nano SMPS); a nanomicro-orifice uniform deposit impactor (nano MOUDI) collected size-resolved samples for gravimetric and chemical analysis. A nanometer tandem differential mobility analyzer (nano TDMA) was used to measure the volatility and hygroscopicity of 4-15 nm particles. These measurements confirm that the particles consisted primarily of sulfates.