11 research outputs found

    Selective Deoxygenation of Allylic Alcohol: Stereocontrolled Synthesis of Lavandulol

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    Selective deoxygenation of allylic alcohol can be successfully carried out by the formation of alkoxyalkyl ether (EE or MOM), followed by Pd(dppe)Cl2-catalyzed reduction with LiBHEt3. (+)-S-Lavandulol has been efficiently synthesized by the application of this protocol to the diol derived from the Pb(OAc)4-promoted oxidative ring-opening of (−)-R-carvone. This deoxygenation method is general and selective for allylic alcohols

    General Preparation and Controlled Cyclization of Acyclic Terpenoids

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    A general preparation method of the all-(E)-polyprenols 12 has been developed from readily available geranyl sulfone by the chain-extension process utilizing the C5 unit 5 and the chain-termination process utilizing the C5 unit 10 together with the chemoselective reductive desulfonylation. The polyprenols 12 were converted to compounds 3 containing two consecutive prenyl sulfone moieties at the tail end, which underwent the controlled electrophilic cyclization only at the carbon−carbon double bonds that were remote from the flat and rigid benzenesulfonyl groups

    Engineering Polyhistidine Tags on Surface Proteins of Acidithiobacillus ferrooxidans: Impact of Localization on the Binding and Recovery of Divalent Metal Cations

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    Metal processing using microorganisms has many advantages including the potential for reduced environmental impacts as compared to conventional technologies.Acidithiobacillus ferrooxidansis an iron- and sulfur-oxidizing chemolithoautotroph that is known to participate in metal bioleaching, and its metabolic capabilities have been exploited for industrial-scale copper and gold biomining. In addition to bioleaching, microorganisms could also be engineered for selective metal binding, enabling new opportunities for metal bioseparation and recovery. Here, we explored the ability of polyhistidine (polyHis) tags appended to two recombinantly expressed endogenous proteins to enhance the metal binding capacity of A. ferrooxidans. The genetically engineered cells achieved enhanced cobalt and copper binding capacities, and the Langmuir isotherm captures their interaction behavior with these divalent metals. Additionally, the cellular localization of the recombinant proteins correlated with kinetic modeling of the binding interactions, where the outer membrane-associated polyHis-tagged licanantase peptide bound the metals faster than the periplasmically expressed polyHis-tagged rusticyanin protein. The selectivity of the polyHis sequences for cobalt over copper from mixed metal solutions suggests potential utility in practical applications, and further engineering could be used to create metal-selective bioleaching microorganisms

    Genetic Modification of Acidithiobacillus ferrooxidans for Rare-Earth Element Recovery under Acidic Conditions

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    As global demands for rare-earth elements (REEs) continue to grow, the biological recovery of REEs has been explored as a promising strategy, driven by potential economic and environmental benefits. It is known that calcium-binding domains, including helix–loop–helix EF hands and repeats-in-toxin (RTX) domains, can bind lanthanide ions due to their similar ionic radii and coordination preference to calcium. Recently, the lanmodulin protein from Methylorubrum extorquens was reported, which has evolved a high affinity for lanthanide ions over calcium. Acidithiobacillus ferrooxidans is a chemolithoautotrophic acidophile, which has been explored for use in bioleaching for metal recovery. In this report, A. ferrooxidans was engineered for the recombinant intracellular expression of lanmodulin. In addition, an RTX domain from the adenylate cyclase protein of Bordetella pertussis, which has previously been shown to bind Tb3+, was expressed periplasmically via fusion with the endogenous rusticyanin protein. The binding of lanthanides (Tb3+, Pr3+, Nd3+, and La3+) was improved by up to 4-fold for cells expressing lanmodulin and 13-fold for cells expressing the RTX domains in both pure and mixed metal solutions. Interestingly, the presence of lanthanides in the growth media enhanced protein expression, likely by influencing protein stability. Both engineered cell lines exhibited higher recoveries and selectivities for four tested lanthanides (Tb3+, Pr3+, Nd3+, and La3+) over non-REEs (Fe2+ and Co2+) in a synthetic magnet leachate, demonstrating the potential of these new strains for future REE reclamation and recycling applications

    Porous TiO<sub>2</sub>/C Nanocomposite Shells As a High-Performance Anode Material for Lithium-Ion Batteries

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    Porous TiO<sub>2</sub>/C nanocomposite shells with high capacity, excellent cycle stability, and rate performance have been prepared. The synthesis involves coating colloidal TiO<sub>2</sub> nanoshells with a resorcinol-formaldehyde (RF) layer with controllable thickness through a sol–gel-like process, and calcining the composites at 700 °C in an inert atmosphere to induce crystallization from amorphous TiO<sub>2</sub> to anatase and simultaneous carbonization from RF to carbon. The cross-linked RF polymer contributes to the high stability of the shell morphology and the porous nature of the shells. A strong dependence of the capacity on the amount of incorporated carbon has been revealed, allowing the optimization of the electrode structure for high-rate cell performance

    Quantifying In-Use PM Measurements for Heavy Duty Diesel Vehicles

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    Heavy duty emissions regulations have recently expanded from the laboratory to include in-use requirements. This paradigm shift to in-use testing has forced the development of portable emissions measurement systems (PEMS) for particulate matter (PM). These PM measurements are not trivial for laboratory work, and are even more complex for in-use testing. This study evaluates five PM PEMS in comparison to UCR’s mobile reference laboratory under in-use conditions. Three on-highway, heavy-duty trucks were selected to provide PM emissions levels from 0.1 to 0.0003 g/hp-h, with varying compositions of elemental carbon (EC), organic carbon (OC), and sulfate. The on-road driving courses included segments near sea level, at elevations up to 1500 m, and coastal and desert regions. The photoacoustic measurement PEMS performed best for the non-aftertreatment system (ATS)-equipped engine, where the PM was mostly EC, with a linear regression slope of 0.91 and an R2 of 0.95. The PEMS did not perform as well for the 2007 modified ATS equipped engines. The best performing PEMS showed a slope of 0.16 for the ATS-equipped engine with predominantly sulfate emissions and 0.89 for the ATS-equipped engine with predominantly OC emissions, with the next best slope at 0.45 for the predominantly OC engine

    Overexpression of AcoP in Acidithiobacillus ferrooxidans for Enhanced Copper Reclamation

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    Copper is an essential critical metal that will be indispensable as we work to reduce our dependence on fossil fuel sources and move to electrification. Here, we explored the cellular overexpression of the AcoP protein to enhance copper binding ability of a representative bioleaching acidophile, Acidithiobacillus ferrooxidans. The engineered cells exhibited enhanced copper binding, regardless of the oxidation state of copper (1.5-fold improvement), as well as in the presence of a nontarget metal, iron (up to 2.7-fold improvement). The acid- and metal-tolerant physiology of A. ferrooxidans enabled the cells to grow in the presence of bottom ash produced from a municipal waste-to-energy facility, and the genetically engineered cells also exhibited enhanced copper recovery (9.5-fold higher selectivity) from this nonconventional feedstock. This work demonstrates a promising proof of concept where bioleaching cells can be modified for the effective reclamation of critical materials from different sources for emerging future applications

    Assessing the Impacts of Ethanol and Isobutanol on Gaseous and Particulate Emissions from Flexible Fuel Vehicles

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    This study investigated the effects of higher ethanol blends and an isobutanol blend on the criteria emissions, fuel economy, gaseous toxic pollutants, and particulate emissions from two flexible-fuel vehicles equipped with spark ignition engines, with one wall-guided direct injection and one port fuel injection configuration. Both vehicles were tested over triplicate Federal Test Procedure (FTP) and Unified Cycles (UC) using a chassis dynamometer. Emissions of nonmethane hydrocarbons (NMHC) and carbon monoxide (CO) showed some statistically significant reductions with higher alcohol fuels, while total hydrocarbons (THC) and nitrogen oxides (NO<sub><i>x</i></sub>) did not show strong fuel effects. Acetaldehyde emissions exhibited sharp increases with higher ethanol blends for both vehicles, whereas butyraldehyde emissions showed higher emissions for the butanol blend relative to the ethanol blends at a statistically significant level. Particulate matter (PM) mass, number, and soot mass emissions showed strong reductions with increasing alcohol content in gasoline. Particulate emissions were found to be clearly influenced by certain fuel parameters including oxygen content, hydrogen content, and aromatics content

    How can we reduce the climate costs of OHBM? A vision for a more sustainable meeting

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    Climate change threatens the future of humanity. It will also significantly impede our ability to conduct science, by destabilising societies globally. Aviation, including travel to scientific conferences, generates a huge carbon footprint. This must be addressed if we are to limit global warming to the 1.5-2C mandated by the Paris agreement of the 2015 UN Climate Change Conference, and time is running very short: we are already at 1.2C of warming. This also means we must urgently transform the way we attend conferences. Although OHBM is only one medium-sized society, it is crucial to recognise that collective action has the power to change social norms, in science, and society more broadly. This has far-reaching consequences beyond the direct carbon savings of updating the meeting format. In this report, authored by the Sustainability and Environment Action Special Interest Group (SEA-SIG), we analysed the carbon footprint of previous Organisation for Human Brain Mapping (OHBM) meetings. On average, attendees travelling to an in-person meeting generate over 10,000 tonnes of carbon – as much as 1250 average German residents would emit over the course of one year (mean of 8t in 2021). Virtually all these emissions are eliminated when we meet online instead. The location of in-person meetings also matters: setting the meeting in a place that requires more colleagues to fly long-haul very significantly increases climate costs by up to three times as much as the lowest-carbon locations. We can do things differently, however. Hybrid meetings - accessible both in-person and online - are set to become the norm for academic societies around the world. Although driven by the COVID-19 pandemic, hybrid meetings should be here to stay, because of the many other benefits they bring to both accessibility and sustainability. There are also several other alternative meeting formats being explored by academic societies, such as a biennial meeting (every other year), and multiple regional hubs, in which attendees travel to their nearest geographical meeting location. Using aviation carbon footprint modelling, we calculated the carbon savings that OHBM would make under these future meeting formats. We also determined the most climate-friendly locations for in-person aspects of future meetings and the least climate-friendly places. As a result, we recommend that all future OHBM meetings are fully hybrid. We furthermore recommend that OHBM transitions to a multiple regional hub model (with hybrid attendance also supported), in locations specifically chosen to minimise long-distance aviation. We do not advocate carbon offsetting as a suitable alternative to tackling real-time and long-term reductions in aviation emissions. We conclude that updating the way OHBM meetings are run for a post-pandemic, climate-crisis-era will save thousands of tonnes of carbon and send a crucial sign at a time of climate emergency. Furthermore, setting the meeting in locations that minimise the need for long-distance flying is critical. Finally, supporting colleagues to attend online and more locally will enhance accessibility, furthering the society’s mission to provide educational forums for the exchange of groundbreaking neuroimaging research. Importantly, as a scientific community we are in an ideal position to lead by example and experiment with new ways of sharing knowledge, including the way we attend conferences

    Additional file 1: Figure S1. of Novel c-Met inhibitor suppresses the growth of c-Met-addicted gastric cancer cells

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    Inhibition Curve. The inhibition percentage was measured in c-Met enzyme assay. The detailed assay procedures are described in Methods. Figure S2. Phosphorylation of Akt and Erk is downregulated by c-Met inhibitors only in c-Met overexpressed cells. SNU-638 (A), SNU-620 (B), SNU-1 (C), or MKN-1 (D) cells were treated with KRC-00509 or crizotinib in dose dependent manner for 3 hr. Cell lysates were prepared for immunoblot with phospho antibodies of c-Met, Akt, and Erk. Tubulin band shows equal loading. Figure S3. Total tyrosine phosphorylations were reduced by c-Met inhibitors in c-Met overexpressed cells. Hs746T (A), or AGS (B) were treated with c-Met inhibitors or crizotinib in dose dependent manner for 3 hr. Cell lysates were prepared for immunoblot with phospho tyrosine antibody. (PPTX 6747 kb
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