Q2 dependence of the neutron spin structure function g2(n) at low Q2

We present the first measurement of the Q2 dependence of the neutron spin structure function g2(n) at five kinematic points covering 0.57 (GeV/c)2 < or = Q2 < or = 1.34 (GeV/c)2 at x approximately = 0.2. Though the naive quark-parton model predicts g2 = 0, nonzero values occur in more realistic models of the nucleon which include quark-gluon correlations, finite quark masses, or orbital angular momentum. When scattering from a noninteracting quark, g2(n) can be predicted using next-to-leading order fits to world data for g1(n). Deviations from this prediction provide an opportunity to examine QCD dynamics in nucleon structure. Our results show a positive deviation from this prediction at lower Q2, indicating that contributions such as quark-gluon interactions may be important. Precision data obtained for g1(n) are consistent with next-to-leading order fits to world data.     

Theory for shock dynamics in particle-laden thin films

We present a theory to explain the emergence of a particle-rich ridge observed experimentally in a thin film particle-laden flow on an incline. We derive a lubrication theory for this system which is qualitatively compared to preliminary experimental data. The ridge formation arises from the creation of two shocks due to the differential transport rates of fluid and particles. This parallels recent findings of double shocks in thermal-gravity-driven flow [A. L. Bertozzi, Phys. Rev. Lett. 81, 5169 (1998); J. Sur, Phys. Rev. Lett. 90, 126105 (2003); A. Munch, Phys. Rev. Lett. 91, 016105 (2003)]. However, here the emergence of the shocks arises from a new mechanism involving the settling rates of the species.     

A library approach to the generation of bisubstrate analogue sulfotransferase inhibitors

[reaction: see text]. A library of potential bisubstrate analogue inhibitors (1) targeting sulfotransferase enzymes was generated by the chemoselective ligation of the PAPS mimic 2 with a panel of 447 aldehydes. Preliminary screening has identified compounds that inhibit estrogen sulfotransferase (EST), an enzyme relevant to breast cancer.     

Reactivity of biarylazacyclooctynones in copper-free click chemistry

The 1,3-dipolar cycloaddition of cyclooctynes with azides, also called "copper-free click chemistry", is a bioorthogonal reaction with widespread applications in biological discovery. The kinetics of this reaction are of paramount importance for studies of dynamic processes, particularly in living subjects. Here we performed a systematic analysis of the effects of strain and electronics on the reactivity of cyclooctynes with azides through both experimental measurements and computational studies using a density functional theory (DFT) distortion/interaction transition state model. In particular, we focused on biarylazacyclooctynone (BARAC) because it reacts with azides faster than any other reported cyclooctyne and its modular synthesis facilitated rapid access to analogues. We found that substituents on BARAC's aryl rings can alter the calculated transition state interaction energy of the cycloaddition through electronic effects or the calculated distortion energy through steric effects. Experimental data confirmed that electronic perturbation of BARAC's aryl rings has a modest effect on reaction rate, whereas steric hindrance in the transition state can significantly retard the reaction. Drawing on these results, we analyzed the relationship between alkyne bond angles, which we determined using X-ray crystallography, and reactivity, quantified by experimental second-order rate constants, for a range of cyclooctynes. Our results suggest a correlation between decreased alkyne bond angle and increased cyclooctyne reactivity. Finally, we obtained structural and computational data that revealed the relationship between the conformation of BARAC's central lactam and compound reactivity. Collectively, these results indicate that the distortion/interaction model combined with bond angle analysis will enable predictions of cyclooctyne reactivity and the rational design of new reagents for copper-free click chemistry.