Photoinduced Selective B-H Activation of nido-Carboranes.

The development of new synthetic methods for B-H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope of boron clusters. Herein, we present a new reaction strategy for the direct site-selective B-H functionalization of nido-carboranes initiated by photoinduced cage activation via a noncovalent cage···π interaction. As a result, the nido-carborane cage radical is generated through a single electron transfer from the 3D nido-carborane cage to a 2D photocatalyst upon irradiation with green light. The resulting transient nido-carborane cage radical could be directly probed by an advanced time-resolved EPR technique. In air, the subsequent transformations of the active nido-carborane cage radical have led to efficient and selective B-N, B-S, and B-Se couplings in the presence of N-heterocycles, imines, thioethers, thioamides, and selenium ethers. This protocol also facilitates both the late-stage modification of drugs and the synthesis of nido-carborane-based drug candidates for boron neutron capture therapy (BNCT).

Positive soil priming effects are the rule at a global scale.

Priming effects of soil organic matter decomposition are critical to determine carbon budget and turnover in soil. Yet, the overall direction and intensity of soil priming remains under debate. A second-order meta-analysis was performed with 9296-paired observations from 363 primary studies to determine the intensity and general direction of priming effects depending on the compound type, nutrient availability, and ecosystem type. We found that fresh carbon inputs induced positive priming effects (+37%) in 97% of paired observations. Labile compounds induced larger priming effects (+73%) than complex organic compounds (+33%). Nutrients (e.g., N, P) added with organic compounds reduced the intensity of priming effects compared to compounds without N and P, reflecting "nutrient mining from soil organic matter" as one of the main mechanisms of priming effects. Notably, tundra, lakebeds, wetlands, and volcanic soils showed much larger priming effects (+125%) compared to soils under forests, croplands, and grasslands (+24…+32%). Our findings highlight that positive priming effects are predominant in most soils at a global scale. Optimizing strategies to incorporate fresh organic matter and nutrients is urgently needed to offset the priming-induced accelerated organic carbon turnover and possible losses.

Hyperaccumulator extracts promoting the phytoremediation of rare earth elements (REEs) by Phytolacca americana: Role of active microbial community in rhizosphere hotspots.

The increased usage of rare earth elements (REEs) leads to the extensive exploitation of rare earth mines, and the REEs pollution in soil caused by the legacy mine tailings has brought great harm to environment and human health. Although Phytolacca americana can remove REEs from contaminated soil to some extent, there is still an urgent problem to improve its efficiency. Hyperaccumulator extract is a new organic material with potential in metal phytoextraction, but its role in REEs phytoremediation and the related underlying processes remain unclear. In this study, hyperaccumulator extracts from P. americana root (PR), stem (PS), leaf (PL) and EDTA were used to improve the phytoremediation efficiency of REEs with P. americana. Soil zymography was applied to assess the enzyme hotspots' spatial distribution in the rhizosphere, and the hotspots' microbial communities were also identified. The results indicated that the application of hyperaccumulator extracts improved the biomass and REEs uptake of P. americana, and the highest REEs content in plant was observed in the treatment of PS, which increased 299% compared to that of the control. Hotspots area of ß-glucosidase, leucine aminopeptidase and acid phosphatase were concentrated in the pant rhizosphere along the roots and increased 2.2, 5.3 and 2.2 times after PS application compared to unamended soils. The PS application increased the relative abundance of Proteobacteria, Cyanobacteria, Bacteroidota and Firmicutes phyla in rhizosphere. Soil fungi have a higher contribution on promoting REEs activation than that of bacteria. Available P and extractable REEs were leading predictors for the plant biomass and REEs concentrations. The co-occurrence network showed that the application of PS creates a more efficient and stable microbial network compared to other treatments. In conclusion, stem-derived hyperaccumulator extract is excellent in stimulating REEs phytoremediation with P. americana by improving hotspots microbial activities and form a healthy rhizosphere microenvironment.

Regio- and stereoselective [3 + 2] cycloaddition reaction: access to isoxazole-dispirobisoxindoles featuring three contiguous stereocenters.

A novel methodology toward the diversity-oriented asymmetric construction of densely functionalized isoxazole-dispirobisoxindoles was developed. This approach is distinguished by an organocatalytic stereo- and appealing ß-regioselective [3 + 2] cycloaddition reaction of 3-methyl-4-nitro-5-isatylidenyl-isoxazoles and 3-isothiocyanato oxindoles. Complex polycyclic oxindoles 3 featuring two different oxindole moieties and three contiguous stereocenters were smoothly afforded in up to 96% yield, 96% ee, and >20 : 1 dr. The described method, which is different from our previous work of α-regioselective asymmetric annulation of 3-methyl-4-nitro-5-isatylidenyl-isoxazoles, is the first ß-regioselective asymmetric annulation.

Thermal-mediated [1,3]-hydrogen transfer as the key step: access to oxindole-chromone hybrid collection with structural diversity.

Inspired by the chemistry and biology of chromone and oxindole derivatives, herein we report the first example of thermal-mediated [1,3]-hydrogen transfer as the key step for the efficient synthesis of oxindole-chromone hybrid collections 2, which avoids additional catalyst and solvent conditions. All the oxindole-chromones 2 are smoothly obtained in >99% yields in all cases, avoiding column chromatography purification. In particular, the products 2 can act as potential synthons for further elaboration in structural diversity, which might be valuable in organic and medicinal chemistry.

The translocation and fractionation of rare earth elements (REEs) via the phloem in Phytolacca americana L.

Rare earth elements (REEs) are considered to be emerging contaminants due to their widespread use and lack of recycling. Phytolacca americana L. has great potential for REEs phytoextraction. Our understanding of REEs in P. americana focuses mostly on root absorption and xylem translocation, but the role of phloem translocation has received little attention. In this research, the translocation and fractionation of REEs from phloem to organs in P. americana were investigated. In addition, the effect of organic acids in the REEs translocation via phloem exudates was also examined. The results showed that REEs could transport bidirectionally via the phloem, and 86% of REEs exported from old leaves could move downwards to the root, whereas only 14% of them transported upwards to the young leaves. Heavy rare earth elements (HREEs) enrichment was found in the REEs fractionation processes both from phloem to leaf and from stem to root, indicating that HREEs were preferentially transferred not only down to roots, but also up to the young leaves. The concentration of oxalic acid in phloem exudates was much higher than other organic acids. 94.7% oxalic acid in phloem exudates was preferred to combine with REEs, especially HREEs. Additionally, the concentrations of HREEs had a high positive correlation with oxalic acid in phloem exudates, which demonstrated oxalic acid may play a significant role in the long-distance transport of HREEs in phloem. In conclusion, HREEs have higher translocation ability than light rare earth elements (LREEs) in both xylem and phloem of P. americana. As far as we know, this is the first report focused on the phloem translocation and redistribution of REEs in P. americana, which provides a valuable understanding of the mechanism for phytoremediation of REEs contaminated soils.

Photoredox B-H functionalization to selective B-N(sp3) coupling of nido-carborane with primary and secondary amines.

Access to nido-carborane site-selective B-N(sp3) coupling by photoredox catalysed B-H activation has been achieved for the first time, which leads to the synthesis of a series of nitrogen-containing nido-carboranes with moderate to good yields. This protocol is applicable to primary and secondary amines containing alkyl, or heteroaryl groups as well as sulfonamides. Furthermore, the open to air and metal-free conditions with excellent site-selectivity represent a significant improvement for B-H functionalization of nido-carboranes with organic functionalities.

[Effect of health education on prevention from schistosome infection in engineering construction workers in Poyang Lake area].

OBJECTIVE: To evaluate the effect of health education on prevention from schistosome infection in engineering construction workers in Poyang Lake area. METHODS: The workers for constructing "De Chang" highway in Poyang Lake area were divided randomly into an experiment group and a control group, "health education + protective skill training" was carried out in the experiment group, whereas, no intervention was implemented in the control group. RESULTS: In the experiment group, the awareness rates of schistosomiasis control knowledge were 7.96% and 96.39% before and after the intervention, respectively; the rates of contacting infested water were 100% and 1.77% pre- and post-intervention, respectively; the work protective rates increased from zero before the intervention to 100% after the intervention; there was no person infected with schistosome after the intervention. However, in the control group, all the indexes above-mentioned had no significant changes. CONCLUSION: The intervention model "health education + protective skill training", can effectively prevent from schistosome infection in engineering construction workers in Poyang Lake area.