Monolithiation of 5,5′‐Dibromo‐2,2′‐bithiophene Using Flow Microreactors: Mechanistic Implications and Synthetic Applications

The lithiation of 5,5′‐dibromo‐2,2′‐bithiophene with one equivalent of an alkyllithium such as n‐BuLi or s‐BuLi was studied by varying the residence time in flow microreactors. With a short residence time, the product 2,2′‐bithiophene (3) derived from dilithiation was obtained preferentially and a significant amount of the starting material 5,5′‐dibromo‐2,2′‐bithiophene remained unchanged. An increase in the residence time caused a higher yield of the product 5‐bromo‐2,2′‐bithiophene derived from monolithiation with expense in the yields of 2,2′‐bithiophene and 5,5′‐dibromo‐2,2′‐bithiophene. The lithiation using MeLi gave the product 5‐bromo‐2,2′‐bithiophene preferentially even with a very short residence time.     

Colour-odour correspondences in women during the menstrual cycle: Comparative analysis between the menstrual and ovulation phases

Women might experience modulation in their perception and cognition of colours and odours during the menstrual cycle, but how women's impressions of and correspondence between colours and odours differ according to the cycle changes remains unknown. Here, we experimentally examined women's performance of several tasks, including evaluation of impressions of colours and odours, matching/nonmatching of colours with odours, and identification of odours, comparing two phases: the beginning of menstruation and ovulation. The results showed that participants had similar impressions of colours and odours and made similar colour choices for odours in both the menstrual and ovulation phases, while “pleasant-unpleasant” impressions of colour and odour might vary according to the menstrual cycle. We found no significant differences in odour identification between the phases. The findings imply that hormonal changes during the menstrual cycle might affect “pleasant-unpleasant” impressions of colour and odour but not other features regarding impressions or crossmodal correspondence. In future studies, examination with a large number of participants is necessary.     

Stochastic model predictive braking control for heavy-duty commercial vehicles during uncertain brake pressure and road profile conditions

When heavy-duty commercial vehicles (HDCVs) must engage in emergency braking, uncertain conditions such as the brake pressure and road profile variations will inevitably affect braking control. To minimize these uncertainties, we propose a combined longitudinal and lateral controller method based on stochastic model predictive control (SMPC) that is achieved via Chebyshev–Cantelli inequality. In our method, SMPC calculates braking control inputs based on a finite time prediction that is achieved by solving stochastic programming elements, including chance constraints. To accomplish this, SMPC explicitly describes the probabilistic uncertainties to be used when designing a robust control strategy. The main contribution of this paper is the proposal of a braking control formulation that is robust against probabilistic friction circle uncertainty effects. More specifically, the use of Chebyshev–Cantelli inequality suppresses road profile influences, which have characteristics that are different from the Gaussian distribution, thereby improving both braking robustness and control performance against statistical disturbances.Additionally, since theKalman filtering (KF) algorithm is used to obtain the expectation and covariance used for calculating deterministic transformed chance constraints, the SMPC is reformulated as a KF embedded deterministic MPC. Herein, the effectiveness of our proposed method is verified via a MATLAB/Simulink and TruckSim co-simulation.     

High-performance molecular-separation ceramic membranes derived from oxidative cross-linked polytitanocarbosilane

Polytitanocarbosilane (TiPCS)-derived ceramic membranes were fabricated using a pre-ceramic polymer. Special attention was focused on a process of thermal-oxidative curing that was used to induce cross-linking and the effect of this process on the ceramic yield, thermal stability, oxidation resistance, and microstructure of TiPCS. The cross-linked TiPCS powders showed a ceramic yield and thermal stability that were higher than that from the non-cross-linked version. In addition, the cross-linked TiPCS with uniform micropores showed higher levels of N₂ and CO₂ adsorption capacity, BET surface area, and micropore volume than the non-cross-linked versions, and the cross-linking process enhanced the stability of the pore structure at high temperature. The cross-linked TiPCS membranes showed high H₂ permeance (1.49 × 10⁻⁶ mol/(m² s Pa)) with sub-nanopores (H₂/SF₆ selectivity: 12 000, H₂/N₂: 10), and in addition higher oxidation resistance than their non-cross-linked counterparts. Furthermore, the influence of the concentration of the TiPCS precursor coating solution was optimized and the hydrothermal stability of the membranes at high temperatures was also evaluated. The optimized membrane demonstrated great performance for the pervaporation removal of methanol in binary azeotropic systems of either MeOH/butyl acetate or MeOH/toluene, and it also showed high hydrothermal stability with excellent dehumidification performance under high temperatures.     

Cesium-adsorption capacity and hydraulic conductivity of sealing geomaterial made with marine clay,bentonite, and zeolite

Great amounts of soil and waste contaminated with radioactive cesium have been generated due to the decontamination work after the Fukushima Daiichi Nuclear Power Plant accident. The aim of this study is to develop a sealing geomaterial for use at the disposal facilities of the soil and waste constructed in the maritime environment. The geomaterial consists of marine clay, bentonite, and zeolite. The hydraulic conductivity and cesium-adsorption performance of the geomaterial were examined through laboratory tests with different proportions of bentonite and zeolite added to marine clay. It was concluded that the hydraulic conductivity could be reduced to the required level by increasing the amount of bentonite and that the cesium-adsorption capacity could be enhanced by increasing the amount of zeolite.     

Small-angle X-ray scattering studies on melting and recrystallization behaviors of poly(oxyethylene) crystallites in poly(d,l-lactide)/poly(oxyethylene) blends

Direct determination of the discrete distribution for crystalline lamellar thickness has been performed for poly(d,l-lactic acid)/poly(oxyethylene) (PDLLA/PEG) blends by conducting small-angle X-ray scattering (SAXS) measurements using synchrotron radiation. The PDLLA used was an random (racemic) copolymer of bio-based poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) with the lactide monomer ratio of l:d = 50:50. It is known that PLA is miscible with PEG in the amorphous state. In the current paper, we report comprehensive results on structural analyses of PDLLA/PEG blends in the course of heating and cooling process using SAXS to elucidate the change in the thickness distribution of the lamellae. As a consequence, it was found that the distribution of the lamellar thickness moves toward the larger value (in other words, lamellar thickening) as temperature approaches the melting point. Typically, the thickness distribution was dispersed in the range of 10–20 nm at room temperature and it changed toward 40 nm in the vicinity of the melting temperature. To the best of our knowledge, this is the first report of direct determination of the discrete distribution for the crystalline lamellar thickness and their in-situ changes in the course of the lamellar thickening process. As a result, the lamellar thickening was found to occur at much lower temperature for the blend samples with 10% and 20% of PDLLA contents as compared to the PEG 100% sample. This phenomenon can be ascribed to the melting point depression owing to the miscibility between PEG and PDLLA. Thereby, thinner lamellae were melted and thicker ones appeared at much lower temperature for the blends than for the PEG 100% sample. As for the average repeating distance (long period) of the lamellar stacks, an abrupt increase similar to the critical divergence was observed (from 25 nm to 50 nm) in the heating process. Not only for the melting behavior but also in the course of recrystallization, change in the lamellar-thickness distribution was uncovered, which shows strong hysteresis depending on what temperature the sample was cooled down from.     

Nonsalt 1‐(arylmethyloxy)pyrene photoinitiators capable of initiating cationic polymerization

Analysis of photoproducts derived from 1‐(methoxynaphthalen‐1‐ylmethyloxy)pyrene initiators and polymer end groups demonstrated that methoxynaphthalen‐1‐ylmethyl carbocation is involved in the initiation steps for both styrene (St) and cyclohexene oxide (CHO) polymerization. Charge transfer from the pyrenyloxy oxygen atom to the methoxynaphthalen‐1‐ylmethyl chromophore in the singlet excited state is assumed to be responsible for the efficient generation of the carbocation species, which also initiates the copolymerization of St and CHO. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40510.     

Boiling heat transfer characteristics of a sulfuric-acid flow in thermochemical iodine–sulfur cycle

The Japan Atomic Energy Agency has been conducting research and development on the thermo-chemical iodine–sulfur (IS) process, which is one of the most attractive water-splitting hydrogen production methods that uses nuclear thermal energy. The sulfuric acid decomposer is one of the key components of the IS process. The boiling heat transfer coefficients of sulfuric acid solutions are required to design the sulfuric acid decomposer. These coefficients were measured in aqueous solutions where the mole fraction of H₂O ranged from 0.17 to 0.37 (heat flux range from 16.9 kW/m² to 5.6 kW/m²) and compared with the empirical correlations formulated for binary mixtures. A combination of the Stephan–Körner correlation, using the empirical constant A₀ = 2.00, and the Nishikawa–Fujita correlation was used to predict the experimental results with an accuracy of ±10%.     

Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.