Making ordered nanostructures in polymers and their thin films is an important technique to produce functional materials. Herein, we report instant yet precise self-assembly systems of amphiphilic random copolymers to build multilayered lamellar structures in bulk materials and thin films. Random copolymers bearing octadecyl groups and hydroxyethyl groups induced crystallization-driven microphase separation via simple evaporation from the solutions to form lamellar structures in the solid state. The domain spacing was controlled in the range between 3.1 and 4.2 nm at the 0.1 nm level by tuning copolymer composition. Interestingly, just by spin-coating the polymer solutions onto silicon substrates, the copolymers autonomously formed thin films consisting of multilayered lamellar structures, where amorphous/hydrophilic parts and crystalline octadecyl domains are alternatingly layered from a silicon substrate to the air/polymer interface at regular intervals. The lamellar domain spacing was tunable by selecting hydrophilic pendants.

Summary C21ORF2 and NEK1 have been identified as amyotrophic lateral sclerosis (ALS)-associated genes. Both genes are also mutated in certain ciliopathies, suggesting that they might contribute to the same signaling pathways. Here we show that FBXO3, the substrate receptor of an SCF ubiquitin ligase complex, binds and ubiquitylates C21ORF2, thereby targeting it for proteasomal degradation. C21ORF2 stabilizes the kinase NEK1, with the result that loss of FBXO3 stabilizes not only C21ORF2 but also NEK1. Conversely, NEK1-mediated phosphorylation stabilizes C21ORF2 by attenuating its interaction with FBXO3. We found that the ALS-associated V58L mutant of C21ORF2 is more susceptible to phosphorylation by NEK1, with the result that it is not ubiquitylated by FBXO3 and therefore accumulates together with NEK1. Expression of C21ORF2(V58L) in motor neurons induced from mouse embryonic stem cells impaired neurite outgrowth. We suggest that inhibition of NEK1 activity is a potential therapeutic approach to ALS associated with C21ORF2 mutation.

No abstract

The first stable neutral stannaaromatic compound, 2-stannanaphthalene , was synthesized by taking advantage of an extremely bulky and efficient steric protection group, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt). The molecular structure and aromaticity of were discussed on the basis of X-ray crystallographic analysis, NMR, UV-vis, and Raman spectroscopy, cyclic voltammetry, and theoretical calculations. 2-Germanaphthalene , which has a framework similar to that of , was synthesized for comparison, and systematic elucidation was made for the properties of 2-metallanaphthalene systems containing a heavier group 14 element (Si, Ge, or Sn).

No abstract

The first stable anthryldiphosphenes, 1 and 2, were synthesized by utilizing kinetic stabilization of 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) groups, and were characterized by spectroscopic and X-ray crystallographic analyses. The UVvisible spectroscopic data suggested the electronic communication between the anthryl moiety and the P=P unit. It was found that TbtP=P(9-Anth) (1a: 9-Anth = 9-anthryl) showed weak fluorescence in hexane solution. Furthermore, the reactivities of anthryldiphosphene 1 with a chromium complex, chalcogenation reagents, a diene, and electron-deficient olefins have been revealed.

All experiments were performed under an argon atmosphere unless otherwise noted. All solvents were purified by standard methods and/or The Ultimate Solvent System (Glass Contour Company) 1 prior to use. 1 H NMR (400 or 300 MHz) and 13 C NMR (100 or 75 MHz) spectra were measured in CDCl 3 or C 6 D 6 with a JEOL JNM AL-400 or JEOL JNM AL-300 spectrometer. A signal due to CHCl 3 (7.25 ppm) or C 6 D 5 H (7.15 ppm) was used as an internal standard in 1 H NMR, and that due to CDCl 3 (77.0 ppm) or C 6 D 6 (128 ppm) was used in 13 C NMR. Multiplicity of signals in 13 C NMR spectra was determined by DEPT technique. High-resolution mass spectral data were obtained on a JEOL JMS-700 spectrometer. UV/vis spectra were measured by JASCO Ubest V-570. GPLC (gel permeation liquid chromatography) was performed on an LC-908 or LC-918 (Japan Analytical Industry Co., Ltd.) equipped with JAIGEL 1H and 2H columns (eluent: toluene or chloroform). Preparative thinlayer chromatography (PTLC) and Wet column chromatography (WCC) were performed with Merck Kieselgel 60 PF254 and Wakogel C-200, respectively. All melting points were determined on a Yanaco micro melting point apparatus and are uncorrected. Elemental analyses were carried out at the Microanalytical Laboratory of the Institute for Chemical Research, Kyoto University. Bis(2bromophenyl)methane, 2 2-bromo-2'-methylbiphenyl, 3 and ArGeCl 3 4 (Ar = Tbt and Bbt) was prepared according to the reported procedures.Synthesis of 9-Bbt-9,10-dihydro-9-germaanthracene (4b).To an ether solution (6 mL) of bis(2-bromophenyl)methane (239 mg, 0.733 mmol) was added n-BuLi (1.58 N in hexane, 1.02 mL, 1.54 mmol) at 0 ºC. After the solution was stirred at 0 ºC for 30 min, an ether solution of BbtGeCl 3 (707 mg, 0.879 mmol) was added at 0 ºC to the reaction mixture. After further stirring at room temperature for 20 h, the reaction mixture was filtered and evaporated. The crude product was purified by GPLC (chloroform), WCC (hexane), and PTLC (hexane : chloroform = 10 : 1) to afford halogermane 3b [286 mg, 43%, 3b (X = Cl) : 3b (X = Br) = 3.8 : 0.5 as judged by 1 H NMR]. To a THF solution of 3b (286 mg, 0.318 mmol) was added LiAlH 4 (36 mg, 0.95 mmol). After

Amphiphilic random and random block terpolymers bearing PEG chains, crystalline octadecyl groups, and amorphous oleyl groups were designed to control crystallization and microphase separation in the solid state.