Search

Herein we report a method for the synthesis of 3,4,5-trisubstituted isoxazoles in water under mild basic conditions at room temperature via a [3 + 2]-cycloaddition of nitrile oxides and 1,3-diketones, β-ketoesters, or β-ketoamides. We optimized the reaction conditions to control the selectivity of the production of isoxazoles and circumvent other competing reactions, such as O-imidoylation or hetero [3 + 2]-cycloaddition. The reaction happens fast in water and completes within 1–2 hours, which provides an environmentally friendly access to 3,4,5-trisubstituted isoxazoles, an important class of structures found in numerous bioactive natural products and pharmaceuticals. Additionally, we optimized the reaction conditions to produce trifluoromethyl-substituted isoxazoles, a prevalent scaffold in biomedical research and drug discovery programs. We also proposed a plausible mechanism for the selectivity of the [3 + 2]-cycloaddition reaction to produce 3,4,5-trisubstituted isoxazoles. Not to be overlooked are our optimized reaction conditions for the dimerization of hydroximoyl chlorides to form furoxans also known as 1,2,5-oxadiazole 2-oxides, a class of structures with important biological activities due to their unique electronic nature and coordination ability.

Agricultural crop productivity relies on the application of chemical pesticides to reduce pest and pathogen damage. However, chemical pesticides also pose a range of ecological, environmental and economic penalties. This includes the development of pesticide resistance by insect pests and pathogens, rendering pesticides less effective. Alternative sustainable crop protection tools should therefore be considered. Semiochemicals are signalling molecules produced by organisms, including plants, microbes, and animals, which cause behavioural or developmental changes in receiving organisms. Manipulating semiochemicals could provide a more sustainable approach to the management of insect pests and pathogens across crops. Here, we review the role of semiochemicals in the interaction between plants, insects and microbes, including examples of how they have been applied to agricultural systems. We highlight future research priorities to be considered for semiochemicals to be credible alternatives to the application of chemical pesticides.

A series of soluble aromatic poly(amide-imide)s (PAIs) was prepared from a new diamide–diamine monomer having biphenyl units with two CF3 groups. The diamide–diamine monomer was polymerized with 2,2′-bis(trifluoromethyl)benzidine and pyromelltic dianhydride through an imidization reaction to prepare PAIs with a controlled imide/amide bond ratio in the main chains. While the PAIs with the highest imide bond content showed a limited solubility, other PAIs were soluble in polar organic solvents and can be solution-cast into flexible freestanding films. All PAIs exhibited high thermal stability with 5% weight loss temperature (Td5) from 464 to 497 °C in air, and no appearance of glass transition up to 400 °C. Notably, the linear coefficient of thermal expansion (CTE) value of the PAI films was linearly decreased with the imide bond content and varied from 44.8 to 7.8 ppm/°C.

In the present study, fiber-reinforced plastics (FRP) grid-reinforced concrete with very rapid hardening polymer (VRHP) mortar composites were fabricated using three types of design methods for the FRP grid (hand lay-up method, resin infusion method, and prepreg oven vacuum bagging method), along with two types of fibers (carbon fiber and glass fiber) and two types of sheets (fabric and prepreg). The FRP grid was prepared by cutting the FRP laminates into a 10 mm thick, 50 mm × 50 mm grid. The tensile behavior of the FRP grid embedded in composites was systematically analyzed in terms of the load extension, fracture mode, partial tensile strain, and load-bearing rate. The CFRP grid manufactured by the prepreg OVB method showed the best tensile behavior compared to the CFRP grid manufactured by the hand lay-up and resin infusion methods. The load-bearing of each grid point was proportional to the height from the load-bearing part when reaching the maximum tensile load. In addition, finite element analysis was conducted to compare the experimental and analysis results.

Soluble and transparent wholly aromatic polyamides (PAs) were synthesized from an unsymmetrical diamine monomer having trifluoromethyl (CF3) groups, 4-(4′-aminophenoxy)-3,5-bis(trifluoromethyl)aniline. The monomer was polymerized with several dicarboxylic acid monomers via the Yamazaki–Higashi polycondensation method. All of the synthesized polyamides have an amorphous morphology, and they are soluble in many polar organic solvents at room temperature. Flexible and transparent films of the polyamides were prepared by solution casting and these polymer films show good optical transparencies with cut-off wavelengths of 337–367 nm and transparencies of 88%–90% at 550 nm. In addition, all the polymers were thermally stable over 400 °C and exhibited glass transition temperatures (Tg) higher than 300 °C. Unsymmetrically inserted trifluoromethyl groups on polyamides improves the solubility as well as the transparency of the polymers while maintaining good thermal properties. They also showed low refractive indices around 1.5333~1.5833 at 633 nm owing to the existence of low polarizable trifluoromethyl groups.

Polyketides are secondary metabolites mainly found in aerobic organisms with wide applications in medicine and agriculture. Here, the authors uncover new polyketides native to the anaerobic bacterium Clostridium acetobutylicum and show their role in triggering sporulation and granulose accumulation.

Abstract In this investigation, electropolishing and plasma ion nitriding are applied to super austenitic stainless steel for the purpose of improving its corrosion and pitting resistance. Electrochemical experiments are conducted with washing water collected directly from the ship’s scrubber. After electropolishing, the surface roughness is improved by about 73.6% compared to mechanical polishing. After plasma ion nitriding, CrN (precipitate), Fe4N (compound), and γN (solid solution) are observed on the surface. The thickness of the layer formed on the surface is measured to be about 10 μm. A hysteresis loop is observed in the cyclic potentiodynamic polarization curves of mechanical polishing and electropolishing, and the areas are calculated as 23.33 mW cm−2 and 0.17 mW cm−2, respectively. The polarization curve of plasma ion nitriding presents perfect passivation characteristics. Accordingly, mechanical polishing and electropolishing reveal local corrosion, whereas plasma ion nitriding presents a tendency towards general corrosion. In the mechanical polishing, electropolishing, and plasma ion nitriding, the corrosion current densities are 0.665 μA cm−2, 0.093 μA cm−2, and 16.47 μA cm−2, respectively, and the maximum damage depth is observed to grow progressively smaller from plasma ion nitriding to electropolishing and then mechanical polishing.

Comparing a solution phase route to a solid phase route in the synthesis of the cytotoxic natural product urukthapelstatin A (Ustat A) confirmed that a solid phase method is superior. The solution phase approach was tedious and involved cyclization of a ridged heterocyclic precursor, while solid phase allowed the rapid generation of a flexible linear peptide. Cyclization of the linear peptide was facile and subsequent generation of three oxazoles located within the structure of Ustat A proved relatively straightforward. Given the ease with which the oxazole Ustat A precursor is formed via our solid phase approach, this route is amenable to rapid analog synthesis.

Abstract Diamond-like carbon (DLC) coating is a surface coating technology with excellent hydrogen permeation resistance and wear resistance. However, it is difficult to completely prevent hydrogen permeation, and when hydrogen penetrates into the coating layer, the DLC coating is adversely affected. Therefore, we investigated the effect of hydrogen embrittlement on the adhesion strength and wear resistance of the DLC coating layer. As the results of the research, the surface roughness of the DLC coating was increased by a maximum of 3.8 times with hydrogen charging, and the delamination ratio of the DLC coating reached about 58%. In addition, the Lc3, which refers to the adhesion strength corresponding to the complete delamination of the DLC coating, was decreased by a maximum of 2.0 N due to hydrogen permeation. In addition, the wear resistance decreased due to hydrogen permeation, and the exposed width of the substrate due to wear increased by more than 4 times. It was also determined that hydrogen blistering or hydrogen-induced cracking occurred at the interface between the DLC coating and the chromium buffer layer due to hydrogen permeation, which decreased the durability of the DLC coating.

Electroless nickel plating is a suitable technology for the hydrogen industry because electroless nickel can be mass-produced at a low cost. Investigating in a complex environment where hydrogen permeation and friction/wear work simultaneously is necessary to apply it to hydrogen valves for hydrogen fuel cell vehicles. In this research, the effects of hydrogen permeation on the mechanical characteristics of electroless nickel-plated free-cutting steel (SUM 24L) were investigated. Due to the inherent characteristics of electroless nickel plating, the damage (cracks and delamination of grain) and micro-particles by hydrogen permeation were clearly observed at the grain boundaries and triple junctions. In particular, the cracks grew from grain boundary toward the intergranualr. This is because the grain boundaries and triple junctions are hydrogen permeation pathways and increasing area of the hydrogen partial pressure. As a result, its surface roughness increased by a maximum of two times, and its hardness and adhesion strength decreased by hydrogen permeation. In particular, hydrogen permeation increased the friction coefficient of the electroless nickel-plated layer, and the damage caused by adhesive wear was significantly greater, increasing the wear depth by up to 5.7 times. This is believed to be due to the decreasing in wear resistance of the electroless nickel plating layer damaged by hydrogen permeation. Nevertheless, the Vickers hardness and the friction coefficient of the electroless nickel plating layer were improved by about 3 and 5.6 times, respectively, compared with those of the free-cutting steel. In particular, the electroless nickel-plated specimens with hydrogen embrittlement exhibited significantly better mechanical characteristics and wear resistance than the free-cutting steel.

The Ni-stanogermanides were formed via an interfacial reaction between Ni film and a Ge1−xSnx (x = 0.083) epilayer grown on a Si substrate driven by thermal treatment, and their microstructural and chemical features were investigated as a function of a rapid thermal annealing (RTA) temperature. The Ni3(Ge1−xSnx) phase was formed at the RTA temperature of 300 °C, above which Ni(Ge1−xSnx) was the only phase formed. The fairly uniform Ni(Ge1−xSnx) film was formed without unreactive Ni remaining after annealing at 400 °C. However, the Ni(Ge1−xSnx) film formed at 500 °C exhibited large surface and interface roughening, followed by the formation of Ni(Ge1−xSnx) islands eventually at 600 °C. The Sn concentration in Ni(Ge1−xSnx) gradually decreased with increasing RTA temperature, implying the enhancement of Sn out-diffusion from Ni(Ge1−xSnx) grains during the Ni-stanogermanidation process at higher temperature. The out-diffused Sn atoms were accumulated on the surface of Ni(Ge1−xSnx), which could be associated with the low melting temperature of Sn. On the other hand, the out-diffusion of Sn atoms from Ni(Ge1−xSnx) along its interface was dominant during the Ni/Ge1−xSnx interfacial reaction, which could be responsible for the segregation of metallic Sn grains that were spatially confined near the edge of Ni(Ge1−xSnx) islands.

A diamond-like carbon (DLC) coating was deposited on the surface of 316L stainless steel using the arc ion plating (AIP) method to improve the life and efficiency of the metallic bipolar plate for polymer electrolyte membrane fuel cells (PEMFCs). The electrochemical characteristics and damage behaviour were investigated in an accelerating solution simulating the PEMFCs operation environment. A result of the experiment showed the corrosion current density of all specimens with DLC coatings was lower than that of the base metal. However, when the thickness of the DLC coating was 0.3 and 0.5 μm, the corrosion resistance was lower than that of the base metal. This is thought to be because defects on the coating surface result in crevice corrosion of the gap between the coating layer and the intermediate layer or between the coating layer and the base metal, further accelerating corrosion. [ABSTRACT FROM AUTHOR]

Polyketides are an important class of bioactive small molecules valued not only for their diverse therapeutic applications, but also for their role in controlling interesting biological phenotypes in their producing organisms. While numerous polyketides are known to be derived from aerobic organisms, only a single family of polyketides has been identified from anaerobic organisms. Here we uncover a family of polyketides native to the anaerobic bacterium Clostridium acetobutylicum, an organism well-known for its historical use as an industrial producer of the organic solvents acetone, butanol, and ethanol. Through mutational analysis and chemical complementation assays, we demonstrate that these polyketides act as chemical triggers of sporulation and granulose accumulation in this strain. This study represents a significant addition to the body of work demonstrating the existence and importance of polyketides in anaerobes, and showcases a strategy of manipulating the secondary metabolism of an organism to improve traits relevant for industrial applications. [ABSTRACT FROM AUTHOR]

Background: The objective of this study was to examine the usefulness of blood cultures and radiologic imaging studies for developing therapeutic strategies in community-acquired acute pyelonephritis (CA-APN) patients. Materials and Methods: We prospectively collected the clinical data of CA-APN patients who visited 11 hospitals from March 2010 to February 2011. Results: Positive urine and blood cultures were obtained in 69.3% (568/820) and 42.7% (277/648), respectively, of a total of 827 CA-APN patients. Blood culture identified the urinary pathogen in 60 of 645 (9.3%) patients for whom both urine and blood cultures were performed; the organisms isolated from urine were inconsistent with those from blood in 11 and only blood cultures were positive in 49 patients. Final clinical failure was more common in the bacteremic patients than the non-bacteremic ones (8.0% vs. 2.7%, P = 0.003), as was hospital mortality (3.6% vs. 0.3%, P = 0.003). Likewise, durations of hospitalization and fever were significantly longer. Bacteremia was independent risk factor for mortality (OR 9.290, 1.145-75.392, P = 0.037). With regard to radiologic studies, the detection rate of APN was 84.4% (445/527) by abdominal computed tomography and 40% (72/180) by abdominal ultrasonography. Eighty-one of 683 patients (11.9%) were found to have renal abscess, perinephric abscess, urolithiasis, hydronephorosis/hydroureter or emphysematous cystitis, which could potentially impact on clinical management. Patients with Pitt score ≥ 1, flank pain or azotemia were significantly more likely to have such structural abnormalities. Conclusion: Blood cultures are clinically useful for diagnosis of CA-APN, and bacteremia is predictive factor for hospital mortality. Early radiologic imaging studies should be considered for CA-APN patients with Pitt scores ≥1, flank pain or azotemia. [ABSTRACT FROM AUTHOR]

The cyclizidine biosynthetic genecluster was identified from StreptomycesNCIB 11649,which revealed the polyketide biosyntheticmachinery for cyclizidine alkaloid biosynthesis. Both in vivomutagenesis study and in vitrobiochemical analysisprovided insight into the timing and mechanism of the biosyntheticenzymes that produce cyclizidine-type indolizidine alkaloids. [ABSTRACT FROM AUTHOR]

It often takes several decades to reach moisture equilibrium state in composite laminates. Therefore, hourly varying fluctuating boundary moisture and temperature conditions require several millions of time steps to reach a state of equilibrium. A new transient analysis method is proposed to efficiently solve moisture distribution of composite laminates with rapidly fluctuating moisture and temperature boundary conditions. First, effective constant diffusivity and maximum moisture content were obtained by averaging transient temperature-dependent moisture diffusivity. In this way, a simple analytic solution can be effectively used to determine the transient moisture distribution under hourly fluctuating boundary conditions. Its efficiencies are demonstrated in three different conditions by comparing this method with a conventional finite difference method. Hygrothermal stress and material degradation were consequently discussed to demonstrate that we must avoid a simple knock-down factor or 40% devastating penalty and use more rational simulation and supporting data. [ABSTRACT FROM AUTHOR]

The Al alloy is environmental friendly, easy to recycle, and provides a high added value to fishing boats. We report a number of electrochemical experiments undertaken to determine the optimum conditions for protecting 5083 Al alloy in seawater. The current density in the cathodic polarization increased with the potential shifts to a more negative value. Current densities in -1.8 V to 2.4 V increased abruptly with any shift toward the active direction. On shifting in more anodic and cathodic directions outside the range from -1.4 V to -0.7 V, the current density increased suddenly. It was concluded that this potential range offered optimal protection potential. [ABSTRACT FROM AUTHOR]

Plasma electrolytic oxidation (PEO) coatings were fabricated on 5083 Al alloy in KOH electrolyte solution with adding various concentrations of Na2SiO3. Changes in voltage–time response and micro-discharge evolution were analyzed, and the surface and cross-section of the resulting coating layer were further characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The results showed that discharge characteristics were evidently changed with different Na2SiO3 concentrations, particularly higher Na2SiO3 concentrations leading to lower dielectric breakdown voltages. It was found that porous surface structure became prevalent with increasing Na2SiO3 concentration. The EDS analysis confirmed the incorporation of Si element in the PEO coatings. The result of XRD analysis revealed that metastable phases such as γ- and η-alumina were produced as a result of PEO, while amorphous phases appeared with excessive Na2SiO3 concentrations (10 and 14 g/L). The coating thickness was significantly increased about 2–8 times with increasing Na2SiO3, almost depending on Na2SiO3 concentration. [ABSTRACT FROM AUTHOR]

In this work, it was investigated that resistance of combination damages of electrochemical corrosion and cavitation-erosion for plasma ion nitrided 18Cr–8Ni–1.1Mn–0.43C stainless steel at various process temperatures under cavitation environment in seawater. The plasma ion nitriding treatment was performed with a gas mixture ratio of 25% N2 and 75% H2 at a temperature of 623, 673, 723, and 773 K for 10 h, at a chamber pressure of 250 Pa. Expanded austenite (γN) was produced at whole plasma ion nitriding temperatures and especially phases of CrN and γ′ were observed at 773 K in X-ray diffraction (XRD) analysis. In Tafel analysis, the highest corrosion potential and corrosion current density were analyzed on the untreated (non-cavitation) specimen among specimens under the cavitation condition. Under cavitation environment, the highest corrosion potential and the lowest corrosion current density presented at 673 K. As a result of observation of surface morphologies after anodic polarization experiment under cavitation environment, uniform corrosion was observed on the untreated specimen and plasma ion nitrided specimens, while localized corrosion was shown on the untreated substrate under non-cavitation environment. Furthermore, greater damage depth and severe morphologies were observed at plasma ion nitrided specimens than untreated substrate, whereas the greatest weight loss at 723 K was indicated due to the high pitting corrosion potential and wide passivity potential region. [ABSTRACT FROM AUTHOR]

The aim of this research is to investigate the optimum plasma ion nitriding temperature on corrosion resistance in natural sea water for plasma ion nitrided 316L stainless steel. Plasma ion nitriding was conducted at different temperatures of 350, 400, 450, and 500 °C with a mixture of 75% of nitrogen and 25% of hydrogen during 10 h. In conclusion of anodic polarization test, a wide passive potential region and a high corrosion potential were observed at a plasma ion nitriding temperature of 450 °C. Moreover, relatively less damage depth and clean surface micrographs were observed at 450 °C as results of observation of three-dimensional (3D) microscope and scanning electron microscope (SEM) after polarization experiments. In addition, higher corrosion potential and lower corrosion current density were indicated at plasma ion nitrided samples than the value of untreated substrate after Tafel analysis. Hence, plasma ion nitrided at 450 °C in sea water solution represented optimum corrosion resistance among the all the plasma ion nitriding temperature parameters. [ABSTRACT FROM AUTHOR]

Afterglow luminescent particles of ZnS:Ag,Co are developed as an efficient light delivery agent for photochemical tissue bonding in deep tissues with prolonged luminescence.

Abstract Background Wilson disease (WD) is a genetic disorder of copper storage, resulting in pathological accumulation of copper in the body. Because symptoms are generally related to the liver, chelating agents capable of capturing excess copper ions after targeted delivery to the liver are highly required for the treatment of WD. Methods We developed hyaluronate-diaminohexane/black phosphorus (HA-DAH/BP) complexes for capturing copper ions accumulated in the liver for the treatment of WD. Results HA-DAH/BP complexes showed high hepatocyte-specific targeting efficiency, selective copper capturing capacity, excellent biocompatibility, and biodegradability. HA enhanced the stability of BP nanosheets and increased copper binding capacity. In vitro cellular uptake and competitive binding tests verified targeted delivery of HA-DAH/BP complexes to liver cells via HA receptor mediated endocytosis. The cell viability test confirmed the high biocompatibility of HA-DAH/BP complexes. Conclusion HA-DAH/BP complexes would be an efficient copper chelating agent to remove accumulated copper in the liver for the WD treatment.

Abstract Diabetic retinopathy is currently treated by highly invasive repeated therapeutic injections and surgical interventions without complete vision recovery. Here, a noninvasive smart wireless far red/near‐infrared (NIR) light emitting contact lens developed successfully for the repeated treatment of diabetic retinopathy with significantly improved compliance. A far red/NIR light emitting diode (LED) is connected with an application‐specific integrated circuit chip, wireless power, and communication systems on a PET film, which is embedded in a silicone elastomer contact lens by thermal crosslinking. After in vitro characterization, it is confirmed that the retinal vascular hyper‐permeability induced by diabetic retinopathy in rabbits is reduced to a statistically significant level by simply repeated wearing of smart far red/NIR LED contact lens for 8 weeks with 120 µW light irradiation for 15 min thrice a week. Histological analysis exhibits the safety and feasibility of LED contact lenses for treating diabetic retinopathy. This platform technology for smart LED contact lens would be harnessed for various biomedical photonic applications.