Nickel‐Catalyzed Suzuki–Miyaura Coupling of a Tertiary Iodocyclopropane with Wide Boronic Acid Substrate Scope: Coupling Reaction Outcome Depends on Radical Species Stability

We describe a nickel‐catalyzed Suzuki–Miyaura arylation of a tertiary iodocyclopropane with arylboronic acids; this is an efficient and convergent strategy for providing various enantioenriched arylcyclopropanes with a quaternary stereogenic center. This is the first metal‐catalyzed coupling between a tertiary alkyl electrophile and a wide range of aromatics, including heteroaromatics. We found that the outcome of the Ni‐catalyzed coupling with halides as electrophiles was dependent on the stability of the radical species formed during the reaction. The use of tert‐butyl alcohol (t‐BuOH) as the reaction solvent was very effective, because of its stability under the radical‐generating reaction conditions.

     

Mouse Gastric Epithelial Cells Resist CagA Delivery by the Helicobacter pylori Type IV Secretion System

The initial step in bacterial infection is adherence of the bacterium to the target cell surface. Helicobacter pylori exploits the interaction of bacterial adhesin protein HopQ with human epithelial CEACAMs (CEACAM1, 5, and 6) to stably adhere to gastric epithelial cells, which is necessary for delivery of the H. pylori CagA oncoprotein into the epithelial cells via a type IV secretion system. In contrast to human CEACAMs, however, HopQ does not interact with Ceacam1 (mouse CEACAM1) in vitro or in CHO cells ectopically expressing Ceacam1. Since the mouse genome lacks Ceacam5 and Ceacam6, no significant HopQ–Ceacam interaction may occur in mouse gastric epithelial cells. Here, we found that the mouse stomach has a much lower expression level of Ceacam1 than the expression level of CEACAM1 in the human stomach. Consistently, mouse gastric epithelial cells resist CagA delivery by cagA-positive H. pylori, and the delivery is restored by ectopic expression of human CEACAM1 or CEACAM5 in mouse gastric epithelial cells. Thus, despite the fact that mice are routinely used for H. pylori infection studies, a low expression level of Ceacam1 in the mouse stomach together with the loss or greatly reduced interaction of HopQ with Ceacams make the mouse an inappropriate model for studying the role of H. pylori-delivered CagA in gastric pathogenesis, including the development of gastric cancer.     

Deposition of Lead Phosphate by Lead-Tolerant Bacteria Isolated from Fresh Water near an Abandoned Mine

Specialist bacteria can synthesize nanoparticles from various metal ions in solution. Metal recovery with high efficiency can be achieved by metal-tolerant microorganisms that proliferate in a concentrated metal solution. In this study, we isolated bacteria (Pseudomonas sp. strain KKY-29) from a bacterial library collected from water near an abandoned mine in Komatsu City, Ishikawa Prefecture, Japan. KKY-29 was maintained in nutrient medium with lead acetate and synthesized hydrocerussite and pyromorphite nanoparticles inside the cell; KKY-29 also survived nanoparticle synthesis. Quantitative PCR analysis of genes related to phosphate metabolism showed that KKY-29 decomposed organic phosphorus to synthesize lead phosphate. KKY-29 also deposited various metal ions and synthesized metal nanoparticles when incubated in various metal salt solutions other than lead. The present study considers the development of biotechnology to recover lead as an economically valuable material.     

Immunomodulatory Properties and Osteogenic Activity of Polyetheretherketone Coated with Titanate Nanonetwork Structures

Polyetheretherketone (PEEK) is a potential substitute for conventional metallic biomedical implants owing to its superior mechanical and chemical properties, as well as biocompatibility. However, its inherent bio-inertness and poor osseointegration limit its use in clinical applications. Herein, thin titanium films were deposited on the PEEK substrate by plasma sputtering, and porous nanonetwork structures were incorporated on the PEEK surface by alkali treatment (PEEK-TNS). Changes in the physical and chemical characteristics of the PEEK surface were analyzed to establish the interactions with cell behaviors. The osteoimmunomodulatory properties were evaluated using macrophage cells and osteoblast lineage cells. The functionalized nanostructured surface of PEEK-TNS effectively promoted initial cell adhesion and proliferation, suppressed inflammatory responses, and induced macrophages to anti-inflammatory M2 polarization. Compared with PEEK, PEEK-TNS provided a more beneficial osteoimmune environment, including increased levels of osteogenic, angiogenic, and fibrogenic gene expression, and balanced osteoclast activities. Furthermore, the crosstalk between macrophages and osteoblast cells showed that PEEK-TNS could provide favorable osteoimmunodulatory environment for bone regeneration. PEEK-TNS exhibited high osteogenic activity, as indicated by alkaline phosphatase activity, osteogenic factor production, and the osteogenesis/osteoclastogenesis-related gene expression of osteoblasts. The study establishes that the fabrication of titanate nanonetwork structures on PEEK surfaces could extract an adequate immune response and favorable osteogenesis for functional bone regeneration. Furthermore, it indicates the potential of PEEK-TNS in implant applications.     

Effects of Aliphatic Alcohols on Formation of Cyclodextrin from Soluble Starch by Bacillus macerans Cyclodextrin Glucanotransferase

Effects of aliphatic alcohols such as ethanol, n-butanol and n-decanol on the formation of cyclodextrin (CD) from soluble starch by Bacillus macerans cyclodextrin glucanotransferase (CGTase) were experimentally studied at 50°C and pH 6.0. The addition of such aliphatic alcohols caused an increase in α-CD yield, which extent was remarkable in n-butanol. From the incubation of α-CD with CGTase, such an increase was found to be due to a restriction on further transglycosylation of α-CD into β-CD by CGTase imposed by the aliphatic alcohols.     

Flexible and Conductive 3D Printable Polyvinylidene Fluoride and Poly(N,N‐dimethylacrylamide) Based Gel Polymer Electrolytes

In this work, 3D printable gel polymer electrolytes (GPEs) based on N,N‐dimethylacrylamide (DMAAm) and polyvinylidene fluoride (PVDF) in lithium chloride containing ethylene glycol solution are synthesized and their physicochemical properties are investigated. 3D printing is carried out with a customized stereolithography type 3D gel printer named “Soft and Wet Intelligent Matter‐Easy Realizer” and free forming GPE samples having variable shapes and sizes are obtained. Printed PVDF/PDMAAm‐based GPEs exhibit tunable mechanical properties and favorable thermal stability. Electrochemical proprieties of the printed GPEs are carried out via impedance spectroscopy in the temperature range of 25–90 °C by varying PVDF content. Ionic conductivity as high as 6.5 × 10^?4 S cm^?1 is achieved at room temperature for GPE containing low PVDF content (5 wt%) and conductivity of the GPEs is increased as temperature rises.     

Electron beam sterilization of cyclo olefin polymer leads to polymer degradation and production of alkyl radicals

We investigated the effects of electron‐beam (EB) sterilization on syringe barrels manufactured from cyclo olefin polymer (COP). The chemical structure of the polymer was determined by interpreting the ¹³C NMR and DEPT‐135 spectra of the COP resin. The antioxidants in the resin were identified by analyzing the liquid chromatography‐photo diode array‐mass spectrometry (LC‐PDA‐MS) data for the methanol extract of the resin and the gas chromatography‐mass spectrometry (GC‐MS) data for the supercritical methanol degradation products of the extract. NMR and LC‐PDA‐MS analyses revealed that EB sterilization produces degradation products in the COP main chain and reduces the quantity of the antioxidants in the COP resin. ESR spectra of the EB‐sterilized syringe barrels indicated the presence and location of alkyl radicals, which were generated in the COP main chain by EB sterilization. ESR analyses also indicated that the quantity of alkyl radicals decreased over time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43498.     

Experimental investigation of melt pool behaviour during selective laser melting by high speed imaging

Melt pool behaviour and the characteristics of the surrounding metal powder during selective laser melting (SLM) are captured using high-speed imaging, and the influence of the substrate temperature and the line building sequence on the formation of the built structure and the generation of spatter particles is experimentally investigated. The results indicate that the substrate temperature has a measurable effect on the formation of droplets and the generation of spatter particles, while the volume specific energy density of the process was the principal factor affecting the built structure.