We study a model of multi-legged catalytic molecular walkers that abstract a class of recently developed synthetic molecular motors. We focus on their kinetics of release of catalytic product, delineating the influence of chemical kinetic parameters, geometric configuration, loss from surface, and bulk kinetics. We show that such walkers can achieve a uniform rate of release over long time scal...

A catalytic asymmetric alkylation of fully substituted enolates with racemic, non-activated secondary alkyl halides is described. The chiral 1,2,3-triazolium ion enables excellent diastereo- and enantiocontrol via enantiofacial discrimination of prochiral enolates and kinetic resolution of secondary halides.

The mechanism of the hydrolytic kinetic resolution (HKR) of terminal epoxides was investigated by kinetic analysis using reaction calorimetry. The chiral (salen)Co-X complex (X = OAc, OTs, Cl) undergoes irreversible conversion to (salen)Co-OH during the course of the HKR and thus serves as both precatalyst and cocatalyst in a cooperative bimetallic catalytic mechanism. This insight led to the i...

Kinetic and thermodynamic studies reveal that the property of significantly enhanced catalytic activity with colloidal stability is attributed to an efficacious means of tuning enzyme-substrate association by varying with the rate constants in the presence of functionalized gold nanoparticles.

Catalytic dynamic kinetic resolution (DKR) of racemic azlactones with EtOD using squaramide-based dimeric cinchona alkaloid organocatalysts is shown to be a highly effective strategy for the preparation of enantiomerically pure α-deuterated chiral α-amino acids.

Many kinetic plasma instabilities, in quite di erent physical systems, share a genuinely similar mathematical structure near isolated phase-space islands. For this reason, dynamical features such as faster-than-exponential growth of the instability, as well as nonlinear frequency sweeping, are found to be universal. Numerical f methods, which follow the evolution of the (nonlinear) perturbed di...

Molecular imaging using PET provides a unique tool for noninvasively investigating the biochemistry of living organs. The wide range of radiolabeled molecules makes it possible to explore various biochemical, physiologic, and pharmacologic processes in vivo. Because each radiotracer is characterized by its particular kinetic behavior in the human body, the quantification of this behavior is a c...

The rhodium-catalyzed intramolecular carboacylation of quinolinyl ketones serves as an ideal subject for the mechanistic study of carbon-carbon bond activation. Combined kinetic and NMR studies of this reaction allowed the identification of the catalytic resting state and determination of the rate law, (12)C/(13)C kinetic isotope effects, and activation parameters. These results have identified...

An integrated approach to the modelling of chemical reactors, particularly catalytic ones is presented. The modelling approach starts from quantum-chemical calculations, mechanistic hypothesis, derivation of kinetic expressions in order to achieve an appropriate kinetic model. The model parameters are determined by regression analysis and the complex behaviour of fixed bed reactors, including c...

Transcription elongation is the process by which RNA polymerase (RNAP) moves along template DNA and synthesizes a complementary RNA. During elongation, RNAP carries out a highly processive and directional net motion, even in the presence of a large external load. From an energetics point of view, RNAP is a molecular motor capable of converting chemical energy derived from NTP hydrolysis into me...