Synthesis of self‐healing polyurethane urea‐based supramolecular materials

Supramolecular polyurethane ureas are expected to have superior mechanical properties primarily due to the reversible, noncovalent interactions such as hydrogen bonding interactions. We synthesized polyurethane prepolymers from small molecular weight of poly(tetramethylene ether)glycol and isophorone diisocyanates, which were end capped with propylamine to synthesize polyurethane ureas with high contents of urea and urethane groups for hydrogen‐bonding formations to facilitate self‐healing. The effects of polyurethane urea molecular weight (3000 ≤ M_n ≤ 9000), crosslinking, and cutting direction were studied in terms of thermal, mechanical, and morphological properties with an emphasis on the self‐healing efficiency. It was found that the thermal self‐healability was more pronounced as the molecular weight of polyurethane urea decreased, showing a maximum of more than 96% with 3000 M_n when the sample was cut along the stretch direction. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 468–474     

Solid‐state 31P NMR investigation on the status of guanine nucleotides in paclitaxel‐stabilized microtubules

Microtubule dynamics is a target for many chemotherapeutic drugs. In order to understand the biochemical effects of paclitaxel on the GTPase activity of tubulin, the status of guanine nucleotides in microtubules was investigated by ³¹P cross‐polarization magic angle spinning (CPMAS) NMR. Microtubules were freshly prepared in vitro in the presence of paclitaxel and then lyophilized in sucrose buffer for solid‐state NMR experiments. A ³¹P CPMAS NMR spectrum with the SNR of 25 was successfully acquired from the lyophilized microtubule sample. The broadness of the ³¹P spectral lines in the spectrum indicates that the molecular environments around the guanine nucleotides inside tubulin may not be as crystalline as reported by many diffraction studies. Deconvolution of the spectrum into four spectral components was carried out in comparison with the ³¹P NMR spectra obtained from five control samples. The spectral analysis suggested that about 13% of the nucleotides were present as GTP and 37% as GDP in the β‐tubulin (E‐site) of the microtubules. It was found that most of the GDPs were present as GDP‐P_i complex in the microtubules, which seems to be one of the effects of paclitaxel binding. Copyright © 2015 John Wiley & Sons, Ltd.     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

Buckling of a stiff thin film on a compliant substrate in large deformation

A finite-deformation theory is developed to study the mechanics of thin buckled films on compliant substrates. Perturbation analysis is performed for this highly nonlinear system to obtain the analytical solution. The results agree well with experiments and finite element analysis in wavelength and amplitude. In particular, it is found that the wavelength depends on the strain. Based on the accurate wavelength and amplitude, the membrane and peak strains in thin films, and stretchability and compressibility of the system are also obtained analytically.     

Bounds to optimal burn‐in and optimal work size

Burn‐in is a widely used method to improve the quality of products or systems after they have been produced. In this paper, we consider the problem of determining the optimal burn‐in time and optimal work size maximizing the long‐run average amount of work saved per time unit in the computer applications. Assuming that the underlying lifetime distribution of the computer has an initially decreasing or/and eventually increasing failure rate function, an upper bound for the optimal burn‐in time is derived for each fixed work size and a uniform (with respect to the burn‐in time) upper bound for the optimal work size is also obtained. Furthermore, it is shown that a non‐trivial lower bound for the optimal burn‐in time can be derived if the underlying lifetime distribution has a large initial failure rate. Copyright © 2005 John Wiley & Sons, Ltd.     

Small and high-density GeSiC dots stacked on buried Ge hut-clusters in Si

Self-assembled GeSiC dots stacked on a Ge hut-cluster layer buried in Si have been investigated. The critical thickness for formation of GeSiC dots is reduced owing to the strain fields from the buried hut-clusters. By utilizing the stacked structure, the dot size is decreased and the uniformity is improved. The highest density of the GeSiC dots with stacked structures is 7.4×10¹⁰ cm⁻², which is six times larger than that of single GeSiC dots. The formation of the self-assembled GeSiC dots is strongly influenced by being stacked with buried Ge dots as well as C incorporation.     

Stereoselective synthesis of (+)-lauthisan

Stereoselective synthesis of (+)-lauthisan has been accomplished starting from d-glyceraldehyde acetonide by combination of diastereoselective alkylation and ring-closing metathesis. High degree of 1,3-asymmetric induction has been realized in ether system.     

Generation of highly stable amidate anion in anionic polymerization of 3‐(triethylsilyl)propyl isocyanate

To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh₄) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh₄, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh₄ as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004     

Sorption of chromium hydroxide sol on silica studied by radiotracing

This study was undertaken to investigate the sorption behavior of chromium hydroxide sol on silica type adsorbent in aqueous solution. Radioisotopic tracer method was used to assess data. This technique allowed sensitive kinetic and equilibrium measurements in both direction: sorption and desorption, which are strongly dependent on solution conditions, such as pH, ionic strength or the presence of complexing species. Total removal of sol particles could not be achieved, even under the most favorable experimental conditions (acidification).     

Intermodulation and noise suppression of a linearized, low-noise hybrid microwave amplifier

A new type of microwave amplifier module, consisting of a solid-state amplifier, a predistortion linearizer, and a traveling-wave-tube (TWT), is realized. Measurements show a noise figure of 2.2 dB at 9.5 GHz and the third-order intermodulation distortion ratio of 53 dBc at 10 dB back off from P1 dB point.