Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Directed Evolution of a Cp*RhIII-Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification

Directed evolution of Cp*Rh^III-linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high-throughput screening (HTS) platform that involves an affinity purification step employing a starch-agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP-tagged biohybrid catalysts in a 96-well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*Rh^III-linked NB(T98H/L100K/K127E) variant with a 4.9-fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.     

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.     

Chemical‐Free Approach for Z‐Isomerization of Lycopene in Tomato Powder: Hot Air and Superheated Steam Heating above the Melting Point of Lycopene

Z‐isomers of lycopene exhibit higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. Therefore, it is important to develop an efficient and environmentally friendly procedure for Z‐isomerization. The current methods for Z‐isomerization of (all‐E)‐lycopene use toxic chemicals such as organic solvents and catalysts. This study is aimed to develop a chemical‐free method for Z‐isomerization of (all‐E)‐lycopene in tomato powder by hot air and superheated steam heating. The Z‐isomerization reaction is promoted by heating above the melting point of lycopene. When heated with superheated steam, the thermal decomposition of lycopene is suppressed compared to that when heated with hot air. When tomato powder is heated at 240 °C for 5 min by superheated steam, the total Z‐isomer content and remaining lycopene are 69.0% and 90.7%, respectively, while with hot air heating, the total Z‐isomer content and remaining lycopene are 69.9% and 68.0%, respectively. These results indicate that the thermal Z‐isomerization of lycopene occurs in the molten state and heating in a low oxygen atmosphere suppresses the thermal decomposition of lycopene. Practical Applications: Tomato powder rich in lycopene Z‐isomers is an important ingredient for the food and animal feed industries. Since Z‐isomers of lycopene are more soluble in solvents including ethanol which is a low‐toxicity and environmentally friendly solvent, the efficiency of lycopene extraction with ethanol can be improved by using the Z‐isomer‐rich tomato powder as a raw material. The obtained Z‐isomer‐rich extract has a high added value because the Z‐isomers have higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. In addition, since lycopene Z‐isomers exhibit higher accumulation efficiency and better color improvement in hen egg yolks than those of the all‐E‐isomer, Z‐isomer‐rich tomato powder is an effective animal feed.     

Modeling of quantitative relationships between physicochemical properties of active pharmaceutical ingredients and tensile strength of tablets using a boosted tree

Objectives: The aim of this study was to explore the potential of boosted tree (BT) to develop a correlation model between active pharmaceutical ingredient (API) characteristics and a tensile strength (TS) of tablets as critical quality attributes.

Methods: First, we evaluated 81 kinds of API characteristics, such as particle size distribution, bulk density, tapped density, Hausner ratio, moisture content, elastic recovery, molecular weight, and partition coefficient. Next, we prepared tablets containing 50% API, 49% microcrystalline cellulose, and 1% magnesium stearate using direct compression at 6, 8, and 10?kN, and measured TS. Then, we applied BT to our dataset to develop a correlation model. Finally, the constructed BT model was validated using k-fold cross-validation.

Results: Results showed that the BT model achieved high-performance statistics, whereas multiple regression analysis resulted in poor estimations. Sensitivity analysis of the BT model revealed that diameter of powder particles at the 10th percentile of the cumulative percentage size distribution was the most crucial factor for TS. In addition, the influences of moisture content, partition coefficients, and modal diameter were appreciably meaningful factors.

Conclusions: This study demonstrates that BT model could provide comprehensive understanding of the latent structure underlying APIs and TS of tablets.     

Effect of Mo on corrosion behavior of Ni20Cr–xMo alloys in air with NaCl–KCl–CaCl2 vapor at 570°C

The effect of Mo on the corrosion behavior of Ni20Cr–xMo alloys in an oxidizing chlorine-containing atmosphere using air mixed with the salt-vapor mixture of NaCl–KCl–CaCl₂ at 570°C was investigated. The results revealed that the corrosion performance of the Ni20Cr alloys in the oxidizing chlorine atmosphere was improved by Mo addition of up to 3 wt%. The Mo-free alloy formed a potassium chromate during corrosion as a result of the reaction between the Cr₂O₃ scale and KCl vapor. The chromate formation increased the chlorine potential at the scale surface and induced the breakdown of the protective Cr₂O₃ scale, resulting in internal chromium chloride precipitates and a Cr-depleted zone. In contrast, the presence of Mo resulted in the formation of a NiO scale, which did not react with the salt vapors and, therefore, prevented the formation of chromates. The beneficial effect of Mo on the high-temperature chlorination of Ni–Cr alloys in salt-vapor-containing atmospheres was ascribed to the suppression of chlorine generation due to NiO scale formation.     

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.