Wen Shang

Cytochrome c on Silica Nanoparticles: Influence of Nanoparticle Size on Protein Structure, Stability, and Activity

The structure, thermodynamic and kinetic stability, and activity of cytochrome c (cyt c) on silica nanoparticles (SNPs) of different sizes have been studied. Adsorption of cyt c onto larger SNPs results in both greater disruption of the cyt c global structure and more significant changes of the local heme microenvironment than upon adsorption onto smaller SNPs. The disruption of the heme microenvironment leads to a more solvent-accessible protein active site, as suggested by Soret circular dichroism spectroscopy and through an increase in peroxidase activity as a function of increased SNP size. Similarly, the stability of cyt c decreases more dramatically upon adsorption onto larger SNPs. These results are consistent with changes in protein-nanoparticle interactions that depend on the size or surface curvature of the supporting nanostructure. This study provides further fundamental insights into the effects of nanoscale surfaces on adsorbed protein structure and function.

Dynamics of ice nucleation on water repellent surfaces.

Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications.

Temperature dependent droplet impact dynamics on flat and textured surfaces

Droplet impact dynamics determines the performance of surfaces used in many applications such as anti-icing, condensation, boiling, and heat transfer. We study impact dynamics of water droplets on surfaces with chemistry/texture ranging from hydrophilic to superhydrophobic and across a temperature range spanning below freezing to near boiling conditions. Droplet retraction shows very strong temperature dependence especially on hydrophilic surfaces; it is seen that lower substrate temperatures lead to lesser retraction. Physics-based analyses show that the increased viscosity associated with lower temperatures combined with an increased work of adhesion can explain the decreased retraction. The present findings serve as a starting point to guide further studies of dynamic fluid-surface interaction at various temperatures.

Influence of substrate elasticity on droplet impact dynamics.

Droplet impact dynamics is vital to the understanding of several phase-change and heat-transfer phenomena. This work examines the role of substrate elasticity on the spreading and retraction behavior of water droplets impacting flat and textured superhydrophobic substrates. Experiments reveal that droplet retraction on flat surfaces decreases with decreasing substrate elasticity. This trend is confirmed through a careful measurement of droplet impact dynamics on multiple PDMS surfaces with varying elastic moduli and comparison with impact dynamics on hard silicon surfaces. These findings reveal that surfaces tend to become more wettable upon droplet impact as the elastic modulus is decreased. First-order analyses are developed to explain this reduced retraction in terms of increased viscoelastic dissipation on soft substrates. Interestingly, superhydrophobic surfaces display substrate-elasticity-invariant impact dynamics. These findings are critical when designing polymeric surfaces for fluid-surface interaction applications.

Chemo- and stereospecific solid-state dimerization of lithium trans-2-butenoate and lithium trans-2-butenoate formamide solvate

60Co γ-irradiation of both lithium trans-2-butenoate (11) and lithium trans-2-butenoate·formamide (12) affords the same dimer, dilithium trans-5-methyl-2-heptenedioate (13). However, stereochemical analysis of products 22 and 24 from the analogous trans-2-butenoate-2-d salts 21 and 23 established that C–C and C–H bond formation occur stereospecifically by syn addition to the double bond in lithiumtrans-2-butenoates 11 and 21 and anti addition to the double bond in lithium trans-2-butenoate·formamide complexes 12 and 23. These reactions, which provide an unprecedented, chemospecific one step synthesis of dicarboxylate 13, add significantly to the synthetic scope of the γ-ray induced reactions of crystalline metal trans-2-butenoates that lead to cyclic and acyclic dimers and acyclic trimers by γ-ray initiated radical chain reactions. The stereochemistry of products 22 and 24 is that predicted by analysis of crystal packing, consistent with least-motion principles of the topochemical postulate as shown in Fig. 12 and 13. Analysis of the crystal structures, with respect to nearest neighbors, is consistent with the hypothesis that formation of carbon–carbon bonds in propagation step 1 and hydrogen atom transfer in propagation step 2 are topochemical and controlled by the crystal lattice. Analysis of the packing diagrams provides a pathway for chain propagation throughout the crystal that consumes all the molecules in the unit cell. The dimerization of 12 is much more rapid and proceeds in much higher yield than that of 11, probably as a result of significantly shorter C⋯C contacts and a more robust pathway for hydrogen transfer.