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.     

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.     

Terpendole E and its Derivative Inhibit STLC‐ and GSK‐1‐Resistant Eg5

Terpendole E is first natural product found to inhibit mitotic kinesin Eg5, but its inhibitory mechanism remains to be revealed. Here, we report the effects of terpendole E and 11ketopaspaline (a new natural terpendole E analogue) on the Eg5–microtubule interaction and in several Eg5 mutants. 11‐Ketopaspaline is a shunt product from terpendole E, and it shows potent inhibitory activity against the microtubule‐stimulated ATPase activity of Eg5. Unlike other Eg5 inhibitors, such as S‐trityl‐L ‐cysteine (STLC) and GSK‐1, both terpendole E and 11‐ketopaspaline only partially inhibited Eg5–microtubule interaction. Furthermore, terpendole E and 11‐ketopaspaline inhibited several Eg5 mutants that are resistant to STLC (Eg5^D130A, Eg5^L214A) or GSK‐1 (Eg5^I299F, Eg5^A356T), but with the same extent of inhibition against wild‐type Eg5. Because Eg5^D130A and Eg5^L214A show cross‐resistance to most known Eg5 inhibitors, which bind the L5 loop, these results suggest that terpendole E and its analogues have a different binding site and/or inhibitory mechanism to those for L5 loop‐binding type Eg5 inhibitors.     

Impact of Serum Chemerin Levels on Liver Functional Reserves and Platelet Counts in Patients with Hepatocellular Carcinoma

Obesity-related metabolic abnormalities, including adipokine imbalance and chronic inflammation, are involved in liver carcinogenesis. Chemerin, a novel adipokine, plays a critical role in adipogenesis, energy metabolism, and inflammation. We evaluated the impact of serum chemerin levels on liver functional reserves in hepatocellular carcinoma (HCC) patients and on the recurrence and prognosis of HCC. This study included 44 patients with any stage of HCC who underwent curative treatment at Gifu Municipal Hospital (Gifu, Japan) between 2006 and 2007. Recurrence-free survival and overall survival were estimated using the Kaplan-Meier method. Serum albumin levels (Pearson’s correlation coefficient; r = 0.3110, p = 0.0399), platelet counts (r = 0.4159, p = 0.0050), and prothrombin times (r = 0.3775, p = 0.0115) were significantly correlated with serum chemerin levels in patients with HCC, and they were inversely correlated with Child-Pugh scores (r = −0.3732, p = 0.0126), serum alanine aminotransferase levels (r = −0.3864, p = 0.0105), and total bilirubin levels (r = −0.4023, p = 0.0068). Among these variables, a multiple comparison test identified that platelet counts and total bilirubin levels were associated with serum chemerin levels (p < 0.0083). No significant correlation was found between serum chemerin levels and recurrence-free survival (p = 0.3691) or overall survival (p = 0.7916). In HCC patients, serum chemerin concentrations were correlated with liver functional reserves and platelet counts, but not with recurrence or prognosis.     

The isothermal conductivity improvement in zirconia-based ceramics under 24 GHz microwave heating

Abstract Under 24-GHz millimetre-wave irradiation heating ionic conductivity of zirconia base ceramics was up to 20 times higher than that of a conventionally-heated sample at the same temperature of 400 °C. The degree of enhancement could be altered by changing the stabilising atom from Y to Yb. Enhancement of ionic conduction was prominent in the setup condition of larger self-heating ratio and larger MMW absorbing materials. The isothermal improvement of ionic conductivity under MMW irradiation would be ascribed to the non-thermal effect.