Rhodium(I)-Catalyzed Defluorinative Bisarylation of Monofluorodienes with Boronic Acids

We herein describe a Rh(I)-catalyzed bisarylation reaction of monofluorodienes using arylboronic acids. Two aryl groups are installed in the trisubstituted (E)-alkene products in one step with excellent diastereoselectivities. An intriguing reaction sequence of Rh(I)-catalyzed 1,6-addition followed by defluorinative coupling is proposed for product formation

Role of the Flavan-3-ol and Galloyl Moieties in the Interaction of (−)-Epigallocatechin Gallate with Serum Albumin

The principal green tea polyphenol, (−)-epigallocatechin-3-<i>O</i>-gallate (EGCg), may provide chemoprotection against conditions ranging from cardiovascular disease to cancer. Binding to plasma proteins stabilizes EGCg during its transport to targeted tissues. This study explored the details EGCg binding to bovine serum albumin. Both fluorescence lifetime and intensity data showed that the hydrophobic pocket between subdomains IIA and IIIA is the binding site for EGCg. Fluorescence and circular dichroism were used to establish the roles of the flavan-3-ol and galloyl moieties of the EGCg in binding and to demonstrate a binding-dependent conformational change in the protein. Competitive binding experiments confirmed the location of binding, and molecular modeling identified protein residues that play key roles in the interaction. This model of EGCg–BSA interactions improves the understanding of the likely physiological fate of this green tea-derived bioactive polyphenol

Solution-Phase Electronegativity Scale: Insight into the Chemical Behaviors of Metal Ions in Solution

By incorporating the solvent effect into the Born effective radius, we have proposed an electronegativity scale of metal ions in aqueous solution with the most common oxidation states and hydration coordination numbers in terms of the effective ionic electrostatic potential. It is found that the metal ions in aqueous solution are poorer electron acceptors compared to those in the gas phase. This solution-phase electronegativity scale shows its efficiency in predicting some important properties of metal ions in aqueous solution such as the aqueous acidities of the metal ions, the stability constants of metal complexes, and the solubility product constants of the metal hydroxides. We have elaborated that the standard reduction potential and the solution-phase electronegativity are two different quantities for describing the processes of metal ions in aqueous solution to soak up electrons with different final states. This work provides a new insight into the chemical behaviors of the metal ions in aqueous solution, indicating a potential application of this electronegativity scale to the design of solution reactions

Phosphorus activators contribute to legacy phosphorus availability in agricultural soils: A review.

Phosphorus (P) is one of the most limiting macronutrients for crop productivity and P deficiency is a common phenomenon in agricultural soils worldwide. Despite long-term application of phosphate fertilizers to increase crop yields, P availability is often low, due to the high affinity of phosphate for the soil solid phase. It has been suggested that the accumulated (surplus) P in agricultural soils is sufficient to sustain crop yields worldwide for about 100years. In this paper, we try to clear up the potential for making use of legacy P in soils for crop growth potentially alleviating the global P resource shortage. Specifically, we try to clear up the potential of soil "P activators" for releasing fixed P. P activators accelerate and strengthen process which transform P into bio-available forms via a range of chemical reactions and biological interactions. They include phosphate solubilizing microorganisms, phosphatase enzymes and enzyme activators, low molecular weight organic acids, humic acids, lignin, crop residues, biochar and zeolites. Although reported performance is variable, there is growing evidence that P activators can promote the release of phosphate from soil and, hence, have potential for mitigating the impending global P crisis. Further basic and applied research is required to better understand the mechanisms of interaction of P activators with natural soils and to maximize activator efficacy

Synergistic Effect of Electrocatalyst for Enhanced Oxygen Reduction Reaction: Low Pt-Loaded CuPt Alloy Nanoparticles Supported on N‑Doped Hierarchical Porous Carbon

It is challenging to synthesize oxygen reduction reaction (ORR) electrocatalysts that are highly efficient, affordable, and stable for use in proton exchange membrane fuel cells. To address this challenge, we developed a low platinum-loading (only 6.68% wt) ORR catalyst (PtCu1-NC), comprising CuPt nanoparticles (average size: 1.51 nm) supported on the N-doped carbon substrates. PtCu1-NC possesses a high specific surface area of 662 m2 g–1 and a hierarchical porous structure, facilitating efficient mass transfer. The synergistic effect from introduced copper and the electron effect from nitrogen modify the electronic structure of platinum, effectively accelerating the ORR reaction and enhancing stability. Density functional theory calculations demonstrate the catalytic mechanism and further verify the synergistic effect. Electrochemical assessments indicate that PtCu1-NC exhibits specific activity and mass activity 5.3 and 5.6 times higher, respectively, than commercial Pt/C. The half-wave potential is 27 mV more positive than that of commercial Pt/C. The electrochemical active surface area value is 104.3 m2 g–1, surpassing that of Pt/C. Approximately 78% of current is retained after 10,000 s chronoamperometry measurement. These results highlight the effectiveness of alloying in improving the catalyst performance

Additional file 1: of Effect of CYP3 A4, CYP3 A5 and ABCB1 gene polymorphisms on the clinical efficacy of tacrolimus in the treatment of nephrotic syndrome

CYP3 A4*1G gene sequencing map (forward sequencing). A: CYP3 A4 *1/*1 (wild type); B: CYP3 A4 *1/*1G (heterozygous type); C: CYP3 A4 *1G/*1G (mutant type). (TIFF 916 kb

Additional file 4: of Effect of CYP3 A4, CYP3 A5 and ABCB1 gene polymorphisms on the clinical efficacy of tacrolimus in the treatment of nephrotic syndrome

ABCB1 G2677T/A gene sequencing map (reverse sequencing). A: ABCB1 2677CC (wild type); B: ABCB1 2677CT (heterozygous type); C: ABCB1 2677CA (heterozygous type); D: ABCB1 2677TT (mutant type); E: ABCB1 2677AT (mutant type); F: ABCB1 2677AA (mutant type). (TIFF 1876 kb

Additional file 3: of Effect of CYP3 A4, CYP3 A5 and ABCB1 gene polymorphisms on the clinical efficacy of tacrolimus in the treatment of nephrotic syndrome

ABCB1 C1236T gene sequencing map (reverse sequencing). A: ABCB1 1236 GG (wild type); B: ABCB1 1236 AG (heterozygous type); C: ABCB1 1236 AA (mutant type). (TIFF 833 kb

Goodness-of-fit for the CD-RISC with different models.

<p>Goodness-of-fit for the CD-RISC with different models.</p

Constructing Optimal Coarse-Grained Sites of Huge Biomolecules by Fluctuation Maximization

Coarse-grained (CG) models are valuable tools for the study of functions of large biomolecules on large length and time scales. The definition of CG representations for huge biomolecules is always a formidable challenge. In this work, we propose a new method called fluctuation maximization coarse-graining (FM-CG) to construct the CG sites of biomolecules. The defined residual in FM-CG converges to a maximal value as the number of CG sites increases, allowing an optimal CG model to be rigorously defined on the basis of the maximum. More importantly, we developed a robust algorithm called stepwise local iterative optimization (SLIO) to accelerate the process of coarse-graining large biomolecules. By means of the efficient SLIO algorithm, the computational cost of coarse-graining large biomolecules is reduced to within the time scale of seconds, which is far lower than that of conventional simulated annealing. The coarse-graining of two huge systems, chaperonin GroEL and lengsin, indicates that our new methods can coarse-grain huge biomolecular systems with up to 10 000 residues within the time scale of minutes. The further parametrization of CG sites derived from FM-CG allows us to construct the corresponding CG models for studies of the functions of huge biomolecular systems