The measurement of rates of initiation in the thermal polymerization of styrene

The thermal initiation of the polymerization of styrene has been studied at temperatures from 60–140°C using DPPH as a free radical scavenger. Rates of free radical formation, measured by the decrease in absorbance at 525 nm, are about seven times greater than those obtained from inhibition period measurements. The difference is probably due to the much greater reactivity of trinitrobenzene derivatives towards diradicals from styrene than towards styryl monoradicals. This view is supported by the different behaviour of the AIBN initiated polymerization of styrene in the presence of DPPH. The thermal initiation process has a low efficiency of initiation and the activation energy is 121 kJ/mole. The results strongly support the diradical mechanism for the thermal initiation of styrene polymerization.     

DNA-templated self-assembly of protein and nanoparticle linear arrays

Self-assembling DNA tiling lattices represent a versatile system for nanoscale construction. Self-assembled DNA arrays provide an excellent template for spatially positioning other molecules with increased relative precision and programmability. Here we report an experiment using a linear array of DNA triple crossover tiles to controllably template the self-assembly of single-layer or double-layer linear arrays of streptavidin molecules and streptavidin-conjugated nanogold particles through biotin-streptavidin interaction. The organization of streptavidin and its conjugated gold nanoparticles into periodic arrays was visualized by atomic force microscopy and scanning electron microscopy.     

Imidazole-based excited-state intramolecular proton-transfer materials: synthesis and amplified spontaneous emission from a large single crystal

We have synthesized a novel class of imidazole-based excited-state intramolecular proton-transfer (ESIPT) materials, i.e., hydroxy-substituted tetraphenylimidazole (HPI) and its derivative HPI-Ac, which formed large single crystals exhibiting intense blue fluorescence and amplified spontaneous emission (ASE). Transparent, clear, and well-defined fluorescent single crystals of HPI-Ac as large as 20 mm x 25 mm x 5 mm were easily grown from its dilute solution. From the X-ray crystallographic analysis and semiempirical molecular orbital calculation, it was deduced that the four phenyl groups substituted into the imidazole ring of HPI and HPI-Ac allowed the crystals free from concentration quenching of fluorescence by limiting the excessive tight-stacking responsible for intermolecular vibrational coupling and relevant nonradiative relaxation. Fluorescence spectral narrowing and efficient ASE were observed in the HPI-Ac single crystal even at low excitation levels attributed to the intrinsic four-level ESIPT photocycle.     

Characterization and epitope mapping of two monoclonal antibodies against human CD99

CD99 plays a critical role in the diapedesis of monocytes, T cell differentiation, and the transport of MHC molecules. Engagement of CD99 by agonistic monoclonal antibodies has been reported to trigger multifactorial events including T cell activation as well as cell-cell adhesion during hematopoietic cell differentiation. In this study, to identify the functional domains participating in the cellular events, we mapped the epitopes of CD99, which are recognized by two agonistic CD99 monoclonal antibodies, DN16 and YG32. Using recombinant fusion proteins of GST with whole or parts of CD99, we found that both antibodies interact with CD99 molecules independently of sugar moieties. DN16 mAb detected a linear epitope located in the amino terminal region of CD99 while YG32 mAb bound another linear epitope in the center of the extracellular domain. To confirm that the identified epitopes of CD99 are actually recognized by the two mAbs, we showed the presence of physical interaction between the mAbs and the fusion proteins or synthetic peptides containing the corresponding epitopes using surface plasmon resonance analyses. The dissociation constants of DN16 and YG32 mAbs for the antigen were calculated as 1.27 x 10(-7) and 7.08 x 10(-9) M, respectively. These studies will help understand the functional domains and the subsequent signaling mechanism of CD99.     

Defect Energetics and Nonstoichiometry in Lanthanum Magnesium Hexaaluminate

Computer-based atomistic simulation methods are applied to address quantitatively the defect energetics and crystal chemistry of lanthanum magnesium hexaaluminate (LMA). The tetrahedral site preference of Mg in the magnetoplumbite structure is determined by calculating lattice energies for different Mg ion distributions. It is revealed that the intrinsic and extrinsic disorders are much influenced by the distribution of Mg in the structure. Our calculations show that oxygen Frenkel disorder is the dominant defect mode to be expected, even though Schottky disorder may also exist. Several feasible defect processes in nonstoichiometric LMA are determined from the enthalpies of the quasi-chemical reactions for the processes with simple point defect energies. We have also modeled some defect complexes in the mirror plane regions. It is found that the Mg ions positioned in the tetrahedral sites suppress the formation of cation vacancies in the mirror plane, through hindering the relaxation of the 12kAl ions by which the vacancies are stabilized. In Mg-deficient nonstoichiometric LMA, however, it is expected that the defect complex [V_La+V_Al+2(V_Al+Al_i)] will be formed in the interspinel layer. Our calculations also indicate that the O_Ladefect is improbable in LMA not only as a simple point defect but also as a member of a defect complex.