Dynamic doping and Cottrell atmosphere optimize the thermoelectric performance of n-type PbTe

High thermoelectric energy conversion efficiency requires a large figure-of-merit, zT, over a broad temperature range. To achieve this, we optimize the carrier concentrations of n-type PbTe from room up to hot-end temperatures by co-doping Bi and Ag. Bi is an efficient n-type dopant in PbTe, often leading to excessive carrier concentration at room temperature. As revealed by density functional theory calculations, the formation of Bi and Ag defect complexes is exploited to optimize the room temperature carrier concentration. At elevated temperatures, we demonstrate the dynamic dissolution of Ag2Te precipitates in PbTe in situ by heating in a scanning transmission electron microscope. The release of n-type Ag interstitials with increasing temperature fulfills the requirement of higher carrier concentrations at the hot end. Moreover, as characterized by atom probe tomography, Ag atoms aggregate along parallel dislocation arrays to form Cottrell atmospheres. This results in enhanced phonon scattering and leads to a low lattice thermal conductivity. As a result of the synergy of dynamic doping and phonon scattering at decorated dislocations, an average zT of 1.0 is achieved in n-type Bi/Ag-codoped PbTe between 400 and 825 K. Introducing dopants with temperature-dependent solubility and strong interaction with dislocation cores enables simultaneous optimization of the average power factor and thermal conductivity, providing a new concept to exploit in the field of thermoelectrics

Conjugation with Acridines Turns Nuclear Localization Sequence into Highly Active Antimicrobial Peptide

The emergence of multidrug-resistant bacteria creates an urgent need for alternative antibiotics with new mechanisms of action. In this study, we synthesized a novel type of antimicrobial agent, Acr3-NLS, by conjugating hydrophobic acridines to the N-terminus of a nuclear localization sequence (NLS), a short cationic peptide. To further improve the antimicrobial activity of our agent, dimeric (Acr3-NLS)2 was simultaneously synthesized by joining two monomeric Acr3-NLS together via a disulfide linker. Our results show that Acr3-NLS and especially (Acr3-NLS)2 display significant antimicrobial activity against gram-negative and gram-positive bacteria compared to that of the NLS. Subsequently, the results derived from the study on the mechanism of action demonstrate that Acr3-NLS and (Acr3-NLS)2 can kill bacteria by membrane disruption and DNA binding. The double targets–cell membrane and intracellular DNA–will reduce the risk of bacteria developing resistance to Acr3-NLS and (Acr3-NLS)2. Overall, this study provides a novel strategy to design highly effective antimicrobial agents with a dual mode of action for infection treatment

Study of the Physiological Dynamics of Cadmium Accumulation in Two Varieties of Rice with Different Cadmium-Accumulating Properties

This study focused on cadmium (Cd) uptake by two rice varieties, Yuzhenxiang (YZX) and Xiangwanxian 12 (XWX), which differ in their capacity to accumulate Cd, i.e., XWX > YZX. Treatments with three different gradients of soil Cd concentrations showed that with the increase in soil Cd concentration gradient, the Cd content in each rice plant organ also increased, i.e., Cd-3 > Cd-2 > Cd-1. The trend in the Cd content of each organ was such that the farther the organ from the root, the lower its Cd content, i.e., root > stem and sheath > leaf > grain. We observed that for all four growth stages, the booting stage is the key stage in terms of Cd absorption, where the highest levels of accumulation are observed, that is, booting stage > full heading stage > tillering stage > maturity stage. Of the two cultivars, XWX had higher SOD, POD, and CAT activities but lower MDA content. In contaminated soils, SOD, POD, and CAT activities increased gradually with the increase in Cd concentration, while MDA content decreased, which indicated that the low Cd variety XWX had an advantage over the high Cd variety YZX. Through the comparative analysis of photosynthetic physiology, it was found that the low-Cd-accumulating rice variety XWX appeared more tolerant to Cd, while the high-Cd-accumulating rice YZX was more sensitive. Therefore, the low Cd rice variety XWX was more suitable for planting safe rice in Cd-polluted paddy fields

Comparative Transcriptomic Analysis of Root Cadmium Responses in Two Chinese Rice Cultivars Yuzhenxiang and Xiangwanxian 12

Cadmium (Cd) pollution in paddy soil is an increasingly serious issue in rice production. It has been reported that there is a higher or lower grain Cd accumulation in the rice cultivars Yuzhenxiang (YZX) or Xiangwanxian 12 (XWX), respectively. To better manage the Cd pollution problem, the genes that might play vital roles in governing the difference in root Cd responses between these two rice cultivars were examined. In this study, the results of RNA sequencing (RNA-seq) showed that there were 341 and 161 differentially expressed genes in the roots of YZX and XWX after Cd exposure, respectively. Among these genes, 7 genes, such as Os06g0196300 (OsJ_019618), Os07g0570700 (OsJ_24808), ADI1, GDCSH, HSFB2C, PEX11-4, and CLPB1, possessed higher degree nodes with each other, through interaction analysis by the STRING (search tool for the retrieval of interacting genes/proteins) software, suggesting that they might play vital roles in Cd response. Based on GO enrichment analysis, 41 differently expressed genes after Cd treatment in YZX or XWX were identified to be related to Cd response. Through comparative transcriptomic analysis, 257 genes might be associated with the root Cd response difference between YZX and XWX. Furthermore, we supposed that ADI1, CFBP1, PEX11-4, OsJ_019618, OsJ_24808, GDCSH, CLPB1, LAC6, and WNK3 might be implicated in Cd response based on the combined analysis of RT-qPCR, interaction, and GO annotation analysis. In conclusion, the numerous genes that might be related to Cd stress response and root Cd response difference between YZX and XWX at the booting stage may be of benefit for the development of rice varieties with low Cd consumption

β-L-Rhamnosylation and β-D-Mannosylation Mediated by 4-O-Ester Groups in Weakly Nucleophilic Environment

Eq-4-O-acyl group directed β-rhamnosylation and β-mannosylation are achieved in carborane or BARF anion formed weakly nucleophilic environment with the assistance of a 2,3-orthocarbonate group. The 4-O-acyl group plays a critical role in directing the β-selectivity, and the weakly coordinating anion is essential to amplify this direction. The orthocarbonate group could be readily removed with 1,3-propanediol in the presence of BF3.Et2O

Catalytic Desymmetrization of <i>meso</i>-Aziridines with Benzofuran-2(3<i>H</i>)‑Ones Employing a Simple In Situ-Generated Magnesium Catalyst

The first example of catalytic desymmetrization of <i>meso</i>-aziridines with benzofuran-2­(3<i>H</i>)-ones is realized by employing a magnesium catalyst utilizing BINOL as a simple and commercially available chiral ligand. Both of the enantiomers of the ring-opening product could be easily accessed by employing (<i>R</i>)- or (<i>S</i>)-BINOL as chiral ligand, respectively. A variety of enantioenriched 3,3-disubstituted benzofuran-2­(3<i>H</i>)-ones containing multiple linear continuous stereocenters were obtained with moderate to good yields, diastereo- and enantioselectivities

Potent Antimicrobial and Antibiofilm Activities of Feleucin-K3 Analogs Modified by α-(4-Pentenyl)-Ala against Multidrug-Resistant Bacteria

The dramatic increase in antimicrobial resistance (AMR) highlights an urgent need to develop new antimicrobial therapies. Thus, antimicrobial peptides (AMPs) have emerged as promising novel antibiotic alternatives. Feleucin-K3 is an amphiphilic α-helical nonapeptide that has powerful antimicrobial activity. In our previous study, it was found that the fourth residue of Feleucin-K3 is important for antimicrobial activity. After α-(4-pentenyl)-Ala was introduced into this position, both the antimicrobial activity and stability were greatly improved. Herein, to improve the limitations of Feleucin-K3, this unnatural amino acid was further introduced into different positions of Feleucin-K3. Among these synthetic Feleucin-K3 analogs, the N-terminal-substituted analog Feleucin-K65 (K65) and C-terminal-substituted analog Feleucin-K70 (K70) had preferable antimicrobial activity. In particular, their antimicrobial activities against multidrug-resistant bacteria were more potent than that of antibiotics. The stabilities of these peptides in salt and serum environments were improved compared with those of Feleucin-K3. In addition, these analogs had low hemolytic activity and AMR. More importantly, they effectively inhibited biofilm formation and exhibited considerable efficacy compared with traditional antibiotics against biofilm infection caused by methicillin-resistant Staphylococcus aureus (MRSA). In antimicrobial mechanism studies, K65 and K70 mainly permeated the outer membrane and depolarized the cytoplasmic membrane, resulting in cellular component leakage and cell death. In summary, analogs K65 and K70 are potential antimicrobial alternatives to solve the antibiotic crisis

Enantioselective Dearomative Arylation of Isoquinolines

The C1-substituted tetrahydroisoquinolines and 1,2-dihydroisoquinoline constitute an important group and are interesting structural motifs found in many natural products and pharmaceuticals. In this context, a phosphoric-acid-catalyzed enantioselective dearomative arylation of isoquinolines was realized, providing the chiral dihydroisoquinolines with indole substituents at the C1-position in good results (up to >99% yield and 97% ee). The reaction features mild reaction conditions and operational simplicity, which make it an attractive approach to the discovery of biologically interesting α-indolisoquinolines

Toward a General Glycosylation Strategy: Exploring the Dual Functions of Acyl Group Direction in Various Nucleophilic Environments

A universal glycosylation strategy could significantly simplify glycoside synthesis. One approach to achieving this goal is through acyl group stereodirecting participation for the corresponding 1,2-, 1,3-, 1,4-, or 1,6-trans glycosylation; how-ever, this approach had been challenging for glycosidic bonds that require distal equatorial-acyl group direction. We have developed an approach in weakly nucleophilic environments for selective 1,4-trans glycosylation directed by the equato-rial-4-O-acyl group. Here, we explored this condition in other distal acyl groups and found, besides stereodirecting partic-ipation, acyl groups also mediated hydrogen bonding between acyl groups and alcohols. The latter showed a diverse ef-fect and classified the acyl group direction into axial and equatorial categories. Corresponding glycosylation conditions were distinguished as guidance for acyl group direction from either category. Hence, the acyl group direction may serve as a general glycosylation strategy

β‑l‑Rhamnosylation and β‑d‑Mannosylation Mediated by 4‑<i>O</i>‑Ester Groups in a Weakly Nucleophilic Environment

eq-4-O-Acyl group directed β-rhamnosylation and β-mannosylation are achieved in a carborane or BARF anion formed weakly nucleophilic environment with the assistance of a 2,3-orthocarbonate group. The 4-O-acyl group plays a critical role in directing the β-selectivity, and the weakly coordinating anion is essential to amplify this direction. The orthocarbonate group could be readily removed with 1,3-propanediol in the presence of BF3·Et2O