Diphenylphosphinylhydroxylamine (DPPH) Affords Late-Stage S-imination to access free-NH Sulfilimines and Sulfoximines.

Sulfilimines, as potential aza-isosteres of sulfoxides, are valued as building blocks, auxiliaries, ligands, bioconjugation handles, and as precursors to versatile S(VI) scaffolds including sulfoximines and sulfondiimines. Here, we report a thioether imination methodology that exploits O-(diphenylphosphinyl)hydroxyl amine (DPPH). Under mild, metal-free, and biomolecule-compatible conditions, DPPH enables late-stage S-imination on peptides, natural products, and a clinically trialled drug, and shows both excellent chemoselectivity and broad functional group tolerance. This methodological report is extended to an efficient and high-yielding one-pot reaction for accessing free-NH sulfoximines with diverse substrates including ones of potential clinical importance. In the presence of a rhodium catalyst, sulfoxides are S-iminated in higher yields to afford free-NH sulfoximines. S-imination was validated on an oxidatively delicate amatoxin to give sulfilimine and sulfoximine congeners. Interestingly, these new sulfilimine and sulfoximine-amatoxins show cytotoxicity. This method is further extended to create sulfilimine and sulfoximine-Fulvestrant and buthionine analogues.

Characterization of gene expression profiles and functional analysis of peptidoglycan recognition protein 2 from rock bream (Oplegnathus fasciatus).

Peptidoglycan recognition protein 2 (PGRP2) is a Zn2+-dependent peptidase that plays important roles in binding to microbial components of the cell membrane, inducing phagocytosis and antimicrobial activity. Rock bream (Oplegnathus fasciatus) PGRP2 (RbPGRP2) was identified in the intestine by next generation sequencing (NGS) analysis. The open reading frame (ORF) the RbPGRP2 cDNA (470 amino acid residues) contains a peptidoglycan recognition protein domain (residues 300 to 446). Alignment analysis revealed that RbPGRP2 shares 37.6-53.5% overall sequence identity with the PGRP2s of other species. Phylogenetic analysis revealed that RbPGRP2 clustered together with PGRP2s from teleosts. In healthy rock bream, RbPGRP2 was found to be ubiquitously expressed in all of the examined tissues, especially in the liver. RbPGRP2 expression was significantly upregulated in all of the examined tissues of rock bream after infection with Edwardsiella piscicida, Streptococcus iniae and red sea bream iridovirus (RSIV) compared with the control. Purified rRbPGRP2 interactions with bacteria and inhibited the growth of bacteria in the presence of Zn2+. These results indicate that RbPGRP2 plays an important role in the innate immune response against bacterial infection.

Piscidin: Antimicrobial peptide of rock bream, Oplegnathus fasciatus.

The piscidin family consists of antimicrobial peptides (AMPs) that are mainly found in fish and are crucial effectors of fish innate immune responses. The piscidin family typically has broad-spectrum antimicrobial activity and can modulate immune responses. In this study, we cloned rock bream piscidin (Rbpisc) and investigated its gene expression and biological activity (including antimicrobial and cytotoxic activities). The coding region of Rbpisc consisted of 213 base pairs (bp) encoding 70 amino acid residues. The tertiary structure predicted for Rbpisc includes an amphipathic helix-loop-helix structure. The Rbpisc gene was highly expressed in the gills of healthy fish. The gene expression of Rbpisc increased in the gills after pathogen infection, while the expression was down-regulated in other tissues. A synthetic peptide based on the AMP 12 domain amino acid sequence of Rbpisc appeared to have broad-spectrum antimicrobial activity against various bacteria. However, the synthetic peptide exhibited weak haemolytic activity against fish erythrocytes. These results suggest that Rbpisc might play an important role in the innate immune responses of rock bream.

In situ field application of electrokinetic remediation for an As-, Cu-, and Pb-contaminated rice paddy site using parallel electrode configuration.

The applicability of an in situ electrokinetic process with a parallel electrode configuration was evaluated to treat an As-, Cu-, and Pb-contaminated paddy rice field in full scale (width, 17 m; length, 12.2 m; depth, 1.6 m). A constant voltage of 100 V was supplied and electrodes were spaced 2 m apart. Most As, Cu, and Pb were bound to Fe oxide and the major clay minerals in the test site were kaolinite and muscovite. The electrokinetic system removed 48.7, 48.9, and 54.5 % of As, Cu, and Pb, respectively, from the soil during 24 weeks. The removal of metals in the first layer (0-0.4 m) was higher than that in the other three layers because it was not influenced by groundwater fluctuation. Fractionation analysis showed that As and Pb bound to amorphous Fe and Al oxides decreased mainly, and energy consumption was 1.2 kWh/m(3). The standard deviation of metal concentration in the soil was much higher compared to the hexagonal electrode configuration because of a smaller electrical active area; however, the electrode configuration removed similar amounts of metals compared to the hexagonal system. From these results, it was concluded that the electrokinetic process could be effective at remediating As-, Cu-, and Pb-contaminated paddy rice field in situ.

In situ electrokinetic remediation of As-, Cu-, and Pb-contaminated paddy soil using hexagonal electrode configuration: a full scale study.

We investigated the in situ applicability of the electrokinetic process with a hexagonal electrode configuration in order to remediate arsenic (As)-, copper (Cu)-, and lead (Pb)-contaminated paddy rice field soil at a field scale (width 17 m, length 12.2 m, and depth 1.6 m). An iron electrode was used in order to prevent the severe acidification of the soil near the anode. We selected ethylenediaminetetraacetic acid (EDTA) as a pursing electrolyte to enhance the extraction of Cu and Pb. The system removed 44.4% of the As, 40.3% of the Cu, and 46.6% of the Pb after 24 weeks of operation. Fractionation analysis showed that the As bound to amorphous ion (Fe) and aluminum (Al) oxyhydroxides was changed into a form of As specifically bound. In the case of Cu and Pb, the fraction bound to Fe-Mn oxyhydroxide primarily decreased. The EDTA formed negatively charged complexes with Cu and Pb, and those complexes were transported toward the anode. The energy consumption was very low compared to that on a small scale because there was less energy consumption due to Joule heating. These results show that the in situ electrokinetic process could be applied in order to remediate paddy rice fields contaminated with multiple metals.

Field application of electrokinetic remediation for multi-metal contaminated paddy soil using two-dimensional electrode configuration.

In this study, we evaluated the feasibility of in situ electrokinetic remediation for arsenic (As)-, copper (Cu)-, and lead (Pb)-contaminated soil, in a pilot-scale field application with two-dimensional electrode configurations. Square and hexagonal configurations with different electrode spacing, 1 m and 2 m, were investigated under a constant 100 V. A square configuration with electrode spacing of 2 m removed 61.5 % of As, 11.4 % of Cu, and 0.9 % of Pb, respectively, and a hexagonal configuration with the same spacing showed a higher removal efficiency in top (59 % of As, 0-0.5 m) and middle (53 % of As, 0.5-1.0 m) layers, but much lower removal efficiency in the bottom layer (1-1.5 m), which was thought to be due to groundwater flow through periodic rise and fall of tides. Fractionation analysis showed that As bound to Fe-Mn oxyhydroxide was the main form of As removed by the electrokinetic process. The two-dimensional configuration wasted less electrical energy by Joule heating, and required fewer electrode installations, compared to the one-dimensional electrode configuration.