The widespread demand of coating, corrosion protection, metallurgy, and microelectronics industries for electrodeposition has been met by developing current successful, commercially-available deposition baths containing metallic salts at higher concentration, highly concentrated supporting electrolytes, and various kinds of organic additives, enabling higher deposition rate, greater current efficiency, and long-term stability for the baths. However, developing effective deposition systems for high-performance electrodeposition is challenging, because, (1) in product point of view, the additives sometimes and rather often cause mechanical and/or electrical problems for deposited metal circuit elements due to inclusion of such additives during deposition process, and, (2) in processing point of view, commercial electrodeposition setups cause huge amount of detrimental effluents that can be a serious environmental and cost problems. These issues may be a product of compromise that is particularly relevant for structure and properties of the deposited metals (film resistivity, surface roughness, mechanical and adhesion strength), and processing (costs and manufacturing steps including rinsing and detrimental effluents treatment). The current solution-based electrodeposition systems are generally incapable of significantly increasing reaction rate (deposition rate constant) form dilute electrolyte solution, because diffusion-limiting current that needs to be higher for industrial manufacturing depends on the concentration (and its gradient) of electrolyte solution, which can be described by Fick’s first law in a steady-state electrodeposition. Additionally, current electrodeposition systems are optimized for large area substrate and mass production manufacturing, thereby cannot be suitable for small-lot, on-demand, and multi-product microfabrication. These have inspired the use of polyelectrolyte membranes to encapsulate metallic ions within inside their channels to concentrate from electrolyte solution while maintaining efficient ion transport properties owing to high density anionic counterparts inside channels and the swelling nature of the membrane.We now show that when the polyelectrolyte membrane does not anchor itself to the cathode substrate, stable electrodeposition of metals on cathode surface is achieved, not as much like a solution-phase electrodeposition, resulting in a new type of solid-state electrodeposition (SED) system (Fig. 1). The SED system consists of cathode electrode, polyelectrolyte membrane (PE), electrolyte solution, and anode electrode.PE works as an additional interfacial phase, in which metal ions are transferred through ion exchange reaction based on concentration gradient of metal ions bound with sulfonic acid functional groups in PE layer. Most important feature of the use of PE at the electrode surface is their ability for metal ions to be concentrated in inner ion transport channels with high density sulfonic anions inside the channels (Fig.1). In the current contribution, we describe transfer process of copper ions between electrodes where the additional PE-solution interfacial layer has been introduced to explain concentration behavior of PE layer for copper ions and electrodeposition characteristics in the present system. From detailed theoretical (both thermodynamic and kinetic) and experimental study regarding with the ion concentration process for PE membrane suggest that (1) the “ion penetration” process is slower than ion exchange (diffusion) process inside PE layer and is therefore rate-determining step for ion concentration, and (2) ion penetration rate increases exponentially as the concentration of copper ions in PE layer decreases.The effect of cation concentration, temperature, and electrochemical deposition conditions on the current efficiency, deposition rate, growth process and morphology of the films has been investigated to optimize the deposition conditions to achieve higher deposition rate. This strategy can be suitable for small-lot, on-demand, and multi-product microfabrication. Figure 1
Clinical feature of heart failure with improved ejection fraction (HFimpEF) remains to be fully elucidated. The present study investigated the association of clinical and echocardiographic parameters with the subsequent improvement of left ventricular ejection fraction (LVEF) in heart failure with reduced ejection fraction (HFrEF).From outpatients with a history of hospitalized for heart failure, 128 subjects diagnosed as HFrEF (LVEF <40%) on heart failure hospitalization were enrolled and longitudinally surveyed. During follow-up periods more than 1 year, 58 and 42 patients were identified as HFimpEF (improved LVEF to ≥40% and its increase of ≥10 points) and persistent HFrEF, respectively.There was no difference in age or sex between the two groups with HFimpEF and persistent HFrEF. The rate of ischemic heart disease was lower and that of tachyarrhythmia was higher in the HFimpEF group than in the persistent HFrEF group. At baseline (i.e., on heart failure hospitalization), LVEF did not differ between the two groups, but left ventricular systolic and diastolic diameters were already smaller and the ratio of early diastolic transmitral velocity to early diastolic tissue velocity (E/e') was lower in the HFimpEF group. A multiple logistic regression analysis revealed that lower baseline E/e' was a significant determinant of HFimpEF, independently of confounding factors such as ischemic heart disease, tachyarrhythmia, and baseline left ventricular dimension.Our findings indicate that the lower ratio of E/e' in the acute phase of heart failure onset is an independent predictor of the subsequent improvement of LVEF in HFrEF patients.
Nanoporous CeO2 was prepared implementing the dealloying method on precursors consisting of Ce–Al alloys characterized by different atomic arrangements. In fact, the atomic arrangement of the precursor alloy strongly influence the surface area of CeO2 in the final product. Nanoporous CeO2 with quite high surface area were formed when an amorphous Ce–Al alloy was used as the precursor. The catalytic performance of the catalyst that Ni was supported on CeO2 prepared from amorphous alloy were evaluated based on the reaction whereby molecular hydrogen is released from ammonia borane. A high level of catalytic activity was observed due to that fine Ni particles were dispersed on CeO2 prepared from amorphous alloy with quite high surface area.
2-Phenylethanol, known for its rose-like odor and antibacterial activity, is synthesized via exogenous phenylpyruvate by the sequential reaction of phenylpyruvate decarboxylase (PDC) and aldehyde reductase. We first targeted ARO10, a phenylpyruvate decarboxylase gene from Saccharomyces cerevisiae, and identified a suitable aldehyde reductase gene. Co-expression of ARO10 and yahK in E. coli transformants yielded 1.1 g/L of 2-phenylethanol in batch culture. We hypothesized that there might be a bottleneck in PDC activity. The computer-based enzyme evolution was utilized to enhance production. The introduction of an amino acid substitution in ARO10 (ARO10 I544W) stabilized the aromatic ring of the phenylpyruvate substrate, increasing 2-phenylethanol yield 4.1-fold compared to wild-type ARO10. Cultivation of ARO10 I544W-expressing E. coli produced 2.5 g/L of 2-phenylethanol with a yield from glucose of 0.16 g/g after 72 h. This approach represents a significant advancement, achieving the highest yield of 2-phenylethanol from glucose using microbes to date.
Abstract Microbial production of mevalonate from renewable feedstock is a promising and sustainable approach for the production of value‐added chemicals. We describe the metabolic engineering of Escherichia coli to enhance mevalonate production from glucose and cellobiose. First, the mevalonate‐producing pathway was introduced into E. coli and the expression of the gene atoB , which encodes the gene for acetoacetyl‐CoA synthetase, was increased. Then, the deletion of the pgi gene, which encodes phosphoglucose isomerase, increased the NADPH/NADP + ratio in the cells but did not improve mevalonate production. Alternatively, to reduce flux toward the tricarboxylic acid cycle, gltA , which encodes citrate synthetase, was disrupted. The resultant strain, MGΔgltA‐MV, increased levels of intracellular acetyl‐CoA up to sevenfold higher than the wild‐type strain. This strain produced 8.0 g/L of mevalonate from 20 g/L of glucose. We also engineered the sugar supply by displaying β‐glucosidase (BGL) on the cell surface. When cellobiose was used as carbon source, the strain lacking gnd displaying BGL efficiently consumed cellobiose and produced mevalonate at 5.7 g/L. The yield of mevalonate was 0.25 g/g glucose (1 g of cellobiose corresponds to 1.1 g of glucose). These results demonstrate the feasibility of producing mevalonate from cellobiose or cellooligosaccharides using an engineered E. coli strain.
