Crowning Proteins: Modulating the Protein Surface Properties using Crown Ethers

Crown ethers are small, cyclic polyethers that have found wide‐spread use in phase‐transfer catalysis and, to a certain degree, in protein chemistry. Crown ethers readily bind metallic and organic cations, including positively charged amino acid side chains. We elucidated the crystal structures of several protein‐crown ether co‐crystals grown in the presence of 18‐crown‐6. We then employed biophysical methods and molecular dynamics simulations to compare these complexes with the corresponding apoproteins and with similar complexes with ring‐shaped low‐molecular‐weight polyethylene glycols. Our studies show that crown ethers can modify protein surface behavior dramatically by stabilizing either intra‐ or intermolecular interactions. Consequently, we propose that crown ethers can be used to modulate a wide variety of protein surface behaviors, such as oligomerization, domain–domain interactions, stabilization in organic solvents, and crystallization.     

Thermally-induced order-order transition of DNA-cationic surfactant complexes

Polyanionic DNA interacts with cationic amphiphiles to form electrostatic complexes exhibiting rich self-assembled structures. This type of complex has been considered as a nonviral carrier in gene therapy and as a template for nanostructure construction. Here we report a thermally-induced phase transition of the complexes of DNA with the mixtures of a cationic surfactant, dodecyltrimethyl bromide (DTAB), and a neutral lipid, dioleoylphosphatidylethanolamine (DOPE), in fully hydrated state. An order-order transition between a multilamellar (L(c)alpha) phase and an inverted hexagonal (H(c)II) phase was found to occur with the transition temperature adjustable by the DTAB-to-DNA base pair molar ratio (x) and DOPE-to-DTAB molar ratio (m). The stability of the L(c)alpha phase was enhanced at lower m and x, as the L(c)alpha-to-H(c)II transition temperature increased with the decreases of these two parameters. The suppression of -to- transition at lower x was attributed to the lower entropic gain from the counterion release due to the presence of uncomplexed DNA in the bulk solution.     

Spin and orbital magnetic moments of Fe3O4

We present measurements of the spin and orbital magnetic moments of Fe3O4 by using SQUID and magnetic circular dichroism in soft x-ray absorption. The measurements show that Fe3O4 has a noninteger spin moment, in contrast to its predicted half-metallic feature. Fe3O4 also exhibits a large unquenched orbital moment. Calculations using the local density approximation including the Hubbard U method and the configuration interaction cluster-model suggest that strong correlations and spin-orbit interaction of the 3d electrons result in the noninteger spin and large orbital moments of Fe3O4.     

Charge-orbital ordering and Verwey transition in magnetite

Local density approximation + Hubbard U (LDA + U) band structure calculations reveal that magnetite (Fe3O4) forms an insulating charge-orbital-ordered state below the Verwey transition temperature. The calculated charge ordering is in good agreement with that inferred from recent experiments. We found an associated t(2g) orbital ordering on the octahedral Fe2+ sublattice. Such an orbital ordering results primarily from the on-site Coulomb interaction. This finding unravels such fundamental issues about the Verwey transition as the mechanism for the charge ordering and for the formation of the insulating gap, as well as the nonobedience of the Anderson's criterion for the charge ordering.     

Optimization of 2‐stage cooperative spectrum for cognitive radio networks using multi‐antenna energy detectors

Cooperative spectrum sensing, a kind of spectrum sensing scheme in cognitive radio (CR), uses multiple CR relays. To increase performance, this study uses multi‐antenna CR relays and beam‐forming reception. The required bandwidth for reporting channels in cooperative spectrum sensing is crucial. Two‐stage cooperative spectrum sensing is proposed to increase performance without increasing the required bandwidth. The cooperative spectrum sensing is also optimized to allow the CR networks to facilitate the best decision‐making. This study determines the detection performance when beam‐forming reception is used. Numerical simulations are used to validate the effectiveness of the method. It is shown that beam‐forming reception outperforms square‐law combining (SLC) for low SNR values. This study proposes a 2‐stage cooperative spectrum sensing method, which uses multi‐antenna CR relays and beam‐forming reception. The cooperative spectrum sensing is also optimized to allow the CR networks to facilitate the best decision‐making. Numerical simulations are used to validate the effectiveness of the method.