Stabilization of atmospheric carbon dioxide via zero emissions-An alternative way to a stable global environment. Part 1: Examination of the traditional stabilization concept

The concept of "stabilization" of atmospheric CO2 concentration is re-examined in connection with climate-change mitigation strategies. A new "zero-emissions stabilization (Z-stabilization)" is proposed, where CO2 emissions are reduced to zero at some time and thereafter the concentration is decreased by natural removal processes, eventually reaching an equilibrated stable state. Simplified climate experiments show that, under Z-stabilization, considerably larger emissions are permissible in the near future compared with traditional stabilization, with the same constraint on temperature rise. Over longer time scales, the concentration and temperature decrease close to their equilibrium values, much lower than those under traditional stabilization. The smaller temperature rise at final state is essential to avoid longer-term risk of sea level rise, a significant concern under traditional stabilization. Because of these advantages a Z-stabilization pathway can be a candidate of practical mitigation strategies as treated in Part 2.(Contributed by Taroh MATSUNO, M.J.A.).     

Requirements for soft magnetic underlayer (SUL)—Micromagnetic simulations of single-pole-type write heads and SUL systems

Landau-Lifshitz-Gilbert micromagnetic models were used to analyze the head field distributions and high-frequency responses for various soft magnetic underlayer thicknesses (t-SUL) and saturation magnetization flux densities (B_s) of single-pole-type (SPT) head-SUL systems. It was found that B_s of 10-12 kG and t-SUL of 30-45 nm would be sufficient for the examined head and perhaps for most next generation head-SUL systems. Antiferromagnetic coupling in the SUL affects the head and SUL magnetization and, eventually, the head field. With regard to the head magnetization response, it was found that the magnetization under the coil responded first, while the response at the main pole tip was quite slow, even compared with the head field. The main pole tip of the head was fully saturated and the main pole yoke was almost saturated, while the SUL was not saturated in the examined head-SUL system.     

Glycine Substitution Effects on the Supramolecular Morphology and Rigidity of Cell-Adhesive Amphiphilic Peptides

Self-assembling peptides that are capable of adopting β-sheet structures can generate nanofibers that lead to hydrogel formation. Herein, to tune the supramolecular morphologies, mechanical properties, and stimuli responses of the hydrogels, we investigated glycine substitution in a β-sheet-forming amphiphilic peptide. Glycine substitution generally enhances conformational flexibility. Indeed, glycine substitution in an amphiphilic peptide weakened the hydrogels or even inhibited the gelation. However, unexpectedly, glycine substitution at the center of the peptide molecule significantly enhanced the hydrogel stiffness. The central glycine substitution affected the molecular packing and led to twisted β-sheet structures and to nanofiber bundling, which likely led to the stiffened hydrogel. Importantly, the supramolecular structures were accurately predicted by molecular dynamics simulations, demonstrating the helpfulness of these techniques for the identification of self-assembling peptides. The hydrogel formed by the amphiphilic peptide with the central glycine substitution had cell adhesive function, and showed a reversible thermal gel-to-sol transition. Thus, glycine substitution is effective in modulating self-assembling structures, rheological properties, and dynamics of biofunctional self-assembling peptides.     

Singly and Doubly Quinoxaline-Fused BIII Subporphyrins

B-Phenyl B^III subporphyrin-α-diones prepared in a three-step reaction sequence from the parent subporphyrin were condensed with 1,2-diaminobenzenes to give the corresponding quinoxaline-fused subporphyrins in variable yields. Quinoxaline-fused B-phenyl-5,10,15-triphenyl B^III subporphyrin was transformed to the corresponding subporphyrin-α-dione in the same three-step reaction sequence, which was then condensed with 1,2-diaminobenzene to give doubly quinoxaline-fused subporphyrin. These quinoxaline-fused subporphyrins exhibit redshifted absorption and fluorescence spectra compared with the parent one. A singly quinoxaline-fused subporphyrin bearing three meso-bis(4-dimethylaminophenyl)aminophenyl substituents shows blueshifted fluorescence in less polar solvent, which has been ascribed to emission associated with charge recombination of intramolecular charge transfer (CT) state.     

Fluorescence Response and Self-Assembly of a Tweezer-Type Synthetic Receptor Triggered by Complexation with Heme and Its Catabolites

There is increasing interest in the development and applications of synthetic receptors that recognize target biomolecules in aqueous media. We have developed a new tweezer-type synthetic receptor that gives a significant fluorescence response upon complexation with heme in aqueous solution at pH 7.4. The synthetic receptor consists of a tweezer-type heme recognition site and sulfo-Cy5 as a hydrophilic fluorophore. The receptor–heme complex exhibits a supramolecular amphiphilic character that facilitates the formation of self-assembled aggregates, and both the tweezer moiety and the sulfo-Cy5 moiety are important for this property. The synthetic receptor also exhibits significant fluorescence responses to biliverdin and bilirubin, but shows very weak fluorescence responses to flavin mononucleotide, folic acid, and nicotinamide adenine dinucleotide, which contain smaller π-scaffolds.     

Fluctuating Carbonaceous Networks with a Persistent Molecular Shape: A Saddle‐Shaped Geodesic Framework of 1,3,5‐Trisubstituted Benzene (Phenine)

A saddle‐shaped macromolecule has been synthesized. The molecule was designed as a geodesic saddle with 1,3,5‐trisubstituted benzene (named phenine) as the fundamental unit. The phenines were woven into a polygonal framework that was composed of 168 sp²‐hybridized carbon atoms. The saddle‐shaped structure with unique symmetry showed atypical conformational changes. The biaryl linkages in this molecule had a small energy barrier for rotation, and these structural fluctuations resulted in seven ¹H NMR resonances representing 84 aromatic hydrogen atoms. Nevertheless, the overall saddle shape of the molecule was persistent, and the “up” and “down” orientations of phenine moieties circulated to give average ¹H resonances. The structural characteristics of this molecule, including the anomalous entropy‐driven dimerization, may deepen our understanding of defect‐rich graphitic sheets.     

Synthesis of dl-coriolin

The total synthesis of dl-coriolin has been achieved in a stereoselective way. The key tricyclic intermediate was synthesized from dicyclopentadiene through a route which involved an S_N2 reaction at a neopentylic position.     

Synthesis of SMP-797: a new potent ACAT inhibitor

A potent ACAT (acyl-CoA: cholesterol acyltransferase) inhibitor SMP-797 was effectively synthesized by the urea formation of 3-amino-4-aryl-1,8-naphthyridin-2(1H)-one and 4-amino-2,6-diisopropylamine. The synthesis of the former compound involved the Suzuki coupling reaction as a key step, and the latter was prepared by the 4-selective nitration of 2,6-diisopropylaniline using 2,3,5,6-tetrabromo-4-methyl-4-nitro-2,5-cyclohexadienone.     

Perfluorophenyl-Directed Giant Porphyrin J-Aggregates

Quadrupolar interactions of porphyrin bearing two pentafluorophenylethynyl terminals ( 1 ) drove the formation of a successive one-dimensional staircase structure, i.e., J-aggregates, to yield millimeter-length needles with a single-crystalline character in methylcyclohexane solution. In contrast, π-stacked interactions of porphyrin bearing two nonfluorinated phenyl terminals ( 2 ) formed no aggregates in solution. A spin-cast film of 1 also showed bathochromic shift of the Soret and Q bands, indicating the formation of J-aggregates. The molecular arrangement of the J-aggregates was revealed by microbeam glazing-incidence wide-angle X-ray diffraction (GIWAXD), and was in good agreement with the optimized structure generated by density functional theory (DFT) calculations.     

SNR improvement by intergranular exchange coupling in CGC perpendicular magnetic recording media

Effect of intergranular exchange coupling in coupled granular and continuous (CGC) perpendicular media was investigated in terms of improvement of signal-to-noise ratio (SNR). The exchange coupling improves SNR and byte error rate (BER); however, it tended to widen the magnetic track width (MWW) of a track. That degradation is of concern for the CGC media. This paper discusses intergranular exchange coupling in CGC media to optimize track density and linear density to achieve high areal density.