Optimization of N fertilizer and synergistic intercropping to enhance the productivity advantage of faba bean and effective control of chocolate spot epidemics.

Intercropping of wheat/faba bean is a common practice within the legume-cereal family. However, the benefits of nitrogen (N) fertilizer optimized synergistic intercropping in improving faba bean productivity while controlling the prevalence of chocolate spot disease have not been established. This study conducted continuous field experiments spanning two planting seasons to investigate two key findings. (1) Optimizing N fertilizer application can enhance the productivity of intercropped faba bean. (2) The percentage severity index (PSI) during the period of maximum prevalence rate (Rmax) of faba bean chocolate spot disease, poses a substantial challenge to faba bean yield. The results indicated that the land equivalent ratio and transgressive overyielding index for each intercropping treatment increased with higher N fertilizer application, exceeding a value of 1, and the land saving proportion also exceeded 0. Intercropping primarily enhances productivity, as measured by the harvest index (HI), by amplifying the complementary effect rather than the selection effect, thus improving the net benefit of intercropping. The HI of single and intercropped faba bean increased with the N1 and N2 treatments in both planting seasons. However, the HI of single and intercropped faba bean at the N3 level decreased significantly, ranging from 17.85% to 29.62%. Furthermore, a notable negative correlation was established between the PSI during critical epidemic (initial epidemic, maximum epidemic rate, and late epidemic) periods and observed and expected faba bean yields. As PSI increased, faba bean yields decreased and PSI of intercropping at different periods were lower than those observed in the single cropping. Additionally, intercropping with the optimized N fertilizer treatment (N2 treatment) exhibited an enhanced relative control effect on chocolate spot disease in faba bean, ranging from 35.21% to 52.36%. This finding confirmed the productivity advantage of intercropping faba bean. In conclusion, this study suggested that optimizing N fertilizer application can enhance the productivity of intercropped faba bean. Wheat/faba bean intercropping effectively controlled the PSI during the period of Rmax, which would otherwise threaten faba bean yield. Consequently, this practice ensured sustained advantages of wheat/faba bean intercropping.

The severity and yield effects of the chocolate spot disease in faba bean affected by intercropping and nitrogen input.

BACKGROUND: The aim is to study the disease suppression efficiency, yield loss rate, and yield benefits of intercropped faba bean against chocolate spot under nitrogen (N) input, to clarify the effectiveness of intercropping faba beans in controlling chocolate spot and its contribution to yield increase. RESULTS: Four N input levels and disease suppression treatments were discovered when faba bean-wheat intercropped was used. Adding N enhanced the chocolate spot's area under disease progression curve (AUDPC) by 27.1-69.9%. In contrast to monoculture, intercropping reduced the AUDPC of the chocolate spot by 32.4-51.0% (P < 0.05). Interestingly, the relative control efficacy (RCE) of intercropping at the EShan site was better. With disease suppression or non-suppression, N input increased grain yield loss and its components in faba bean. The total yield advantage effect (TE) and disease-suppression effect (DSE) of faba bean intercropped at the two experimental sites were significantly increased under N input (N1 and N2 level). The proportion of recovery yield due to intercropping suppressed disease (DSE/TE ratio) in EShan (52.1%) was higher than that in Xundian (40.9%), and the DSE of intercropping played an indispensable role in the two sites. Regression analysis of AUDPC and grain yield loss amount showed that one unit increase in chocolate spot AUDPC could cause a grain yield loss of 0.38-0.86 kg ha-1 . The partial land equivalent ratio (pLER) of intercropping faba beans at the EShan site was > 0.33. CONCLUSION: In conclusion, intercropped faba bean with N treatment (45-90 kg ha-1 ) was the best choice for maximizing the intercropping disease control effect. © 2023 Society of Chemical Industry.

Mechanistic Studies Yield Improved Protocols for Base-Catalyzed Anti-Markovnikov Alcohol Addition Reactions.

The catalytic anti-Markovnikov addition of alcohols to simple alkenes is a longstanding synthetic challenge. We recently disclosed the use of organic superbase catalysis for the nucleophilic addition of alcohols to activated styrene derivatives. This article describes mechanistic studies on this reversible reaction, including thermodynamic and kinetic profiling as well as computational modeling. Our findings show the negative entropy of addition is counterbalanced by an enthalpy that is most favored in nonpolar solvents. However, a large negative alcohol rate order under these conditions indicates excess alcohol sequesters the active alkoxide ion pairs, slowing the reaction rate. These observations led to an unexpected solution to a thermodynamically challenging reaction: use of less alcohol enables faster addition, which in turn allows for lower reaction temperatures to counteract Le Chatelier's principle. Thus, our original method has been improved with new protocols that do not require excess alcohol stoichiometry, enable an expanded alkene substrate scope, and allow for the use of more practical catalyst systems. The generality of this insight for other challenging hydroetherification reactions is also demonstrated through new alkenol cyclization and oxa-Michael addition reactions.

Intercropping of Faba Bean with Wheat Under Different Nitrogen Levels Reduces Faba Bean Rust and Consequent Yield Loss.

While intercropping can help control faba bean rust, the ability of intercropping to reduce this disease under different levels of nitrogen fertilization and its contribution to increasing yield is not clear. In this study, two planting patterns of faba bean monocropping and wheat/faba bean intercropping, together with two treatments for disease control and noncontrol, and four nitrogen application levels (N0 [0 kg/ha], N1 [45 kg/ha], N2 [90 kg/ha], and N3 [135 kg/ha]) were tested for 2 years in a continuous field experiment. The results revealed that nitrogen application increased the area under the disease progress curve (AUDPC) of faba bean rust from 41.9 to 47.3%, with the N3 treatment resulting in the largest increase. Nitrogen application decreased the relative control efficacy of intercropping on faba bean rust. Compared with monocropping, N0 to N3 with intercropping significantly reduced AUDPC by 33.1% for the first year and 28.7% for the second year (P < 0.05). Nitrogen application aggravated the faba beans grain yield loss, while the loss of yield components increased in the first year and then declined as the nitrogen application increased; the yield losses of monocropping were higher than those of intercropping. The N1 and N2 application levels significantly increased the total effect (TE) of intercropping yield advantage by 34.3 and 32.9% in the 2 years, respectively. During the 2 years, the overall partial land equivalent ratio of faba bean was greater than 0.33. The average disease control effect (DCE)/TE of intercropping was 56.1 and 49.3% for the 2 years, respectively, indicating that intercropping increased yields and that the contribution of the DCE was close to or higher than that of the other intercropping effects. A regression analysis of the grain yield loss and the AUDPC showed that reducing the nitrogen fertilizer input (N1) could effectively reduce the yield loss caused by rust and enhance the yield. Intercropping of faba bean combined with a suitable nitrogen application (45 kg/ha) is the best treatment to maximize yield by fully utilizing intercropping for managing faba bean rust.

Selective Defluoroallylation of Trifluoromethylarenes.

We report a fluoride-initiated coupling reaction between trifluoromethylarenes and allylsilanes to access allylated α,α-difluorobenzylic compounds. This method's utility is demonstrated through a 30 mmol scale reaction, a sequential allylation/derivatization protocol and multiple examples of site-selective trifluoromethylarene allylation. Initial mechanistic studies suggest a base-induced single electron transfer pathway is responsible for the high efficiency and selectivity of this novel C-F substitution process.

Superbase-Catalyzed anti-Markovnikov Alcohol Addition Reactions to Aryl Alkenes.

The organic superbase P4- t-Bu catalyzes the direct anti-Markovnikov addition of alcohols to aryl alkenes to access valuable ß-phenethyl ethers. A diverse substrate scope of aryl alkenes and alcohols is demonstrated, including heterocyclic systems and unprotected aminoalcohols. Mechanistic studies reveal that the reaction is under equilibrium control and extensive comparisons to common inorganic bases indicate that the broad reaction scope is uniquely enabled through the use of the organic superbase.

Combined Iron/Hydroxytriazole Dual Catalytic System for Site Selective Oxidation Adjacent to Azaheterocycles.

This report details a new method for site-selective methylene oxidation adjacent to azaheterocycles. A dual catalysis approach, utilizing both an iron Lewis acid and an organic hydroxylamine catalyst, proved highly effective. We demonstrate that this method provides complementary selectivity to other known catalytic approaches and represents an improvement over current heterocycle-selective reactions that rely on stoichiometric activation.

A highly diastereo- and enantioselective synthesis of tetrahydroquinolines: quaternary stereogenic center inversion and functionalization.

Tetrahydroquinolines containing two quaternary stereogenic centers were synthesized with excellent ee and dr via a four-component cyclization reaction catalyzed by a chiral phosphoric acid. High chemoselectivity was achieved by differentiating anilines with similar reactivities to yield diverse "hybrid" products. The chirality of the quaternary C4 atom of the 4-aminotetrahydroquinoline products was found to undergo highly stereoselective inversion, enabling facile functionalization using a wide range of nucleophiles (C, O, N, and S).

Effects of Applied Ratio of Nitrogen on the Light Environment in the Canopy and Growth, Development and Yield of Wheat When Intercropped.

Changes in the light environment have an important effect on crop growth and yield. To clarify the effects of intercropping and the application of nitrogen on the yield of wheat and light within the crop canopy, the relationship between light and yield and their response to nitrogen fertilizer were studied. In a 2-year field experiment, the characteristics of growth, light, biomass, and yield of wheat were measured using three cropping arrangements (monocropped wheat, monocropped faba beans, and intercropped wheat/faba beans) and four levels of applied nitrogen, in groups termed N0 (0 kg/ha), N1 (90 kg/ha), N2 (180 kg/ha), and N3 (270 kg/ha). The results demonstrated that the application of nitrogen fertilizer increased wheat plant height, spike leaf length and width, and the number of leaves while significantly decreasing wheat canopy light transmittance (LT) and canopy photosynthetic active radiation transmittance (PART), by 7.5-71.1 and 12.7-75.1%, respectively. There was a significantly increased canopy photosynthetic active radiation interception rate (IPAR) of 7.5-97.8% and an increase in biomass of 9.6-38.4%, of which IPAR, biomass, and yield were highest at the N2 level. Compared with monocropping, intercropping increased parameters of wheat growth to varying degrees. Intercropping decreased LT and PART by 10.8-46.4 and 15.7-58.7%, respectively, but increased IPAR by 0.1-66.0%, wheat biomass and yield by 7.5-17.4 and 27.7-47.2%, respectively. The mean yield of intercropped wheat increased by 35.8% over 2 years, while the mean land equivalent ratio (LER) was 1.36, for which a values greater than 1 indicates that wheat and faba bean intercropping is advantageous. Correlation analysis demonstrated that there was a very significant negative correlation between wheat LT and yield, while simultaneously demonstrating a very significant positive correlation between PART and IPAR with yield, indicating that the efficient interception and utilization of light energy in intercropping was the basis for the higher biomass and yield of wheat. In summary, wheat/faba bean intercropping and the application of nitrogen at 180 kg/ha were effective in increasing wheat yield.

Effects of Nitrogen and Intercropping on the Occurrence of Wheat Powdery Mildew and Stripe Rust and the Relationship With Crop Yield.

Wheat powdery mildew (Blumeria graminis f. sp. tritici) and stripe rust (Puccinia striiformis Westend f. sp. tritici) restrict wheat production in southwest China. Nitrogen fertilizers may influence outbreaks of these wheat diseases where wheat/faba beans are intercropped. To clarify how intercropping and varying nitrogen levels influence wheat powdery mildew and stripe rust and their relationship with crop yield, two consecutive field experiments were conducted from 2015 to 2017. Three cropping regimens (monocropped wheat, monocropped faba beans, and intercropped wheat/faba beans) and four nitrogen levels [N0 (0 kg⋅ha-1), N1 (90 kg⋅ha-1), N2 (180 kg⋅ha-1), and N3 (270 kg⋅ha-1)] were evaluated. In two consecutive planting seasons, the incidence and disease index of powdery mildew and stripe rust increased, while the disease index was more affected by nitrogen levels than their incidence. Both diseases were most prevalent at the N3 level. Compared with monocropping, intercropping (N0-N3 levels) reduced the incidence of powdery mildew by 2.8-37.0% and disease index by 15.5-47.4%, increased the relative control effect by 10.7-56.2 and 16.3-47.2%, reduced the incidence of stripe rust by 2.9-42.7% and disease index by 8.3-42.2%, and increased the relative control effect by 5.9-43.7 and 8.8-42.1%. The relative control efficacy of intercropping was most affected by N2 level. Intercropping yield increased with increasing nitrogen by 25.0-46.8%, and overall land equivalent ratio (LER) was 1.30-1.39. The correlation coefficient between disease index and wheat yield for both diseases was -0.7429 to -0.9942, a significant negative correlation, most significant at N1. Nitrogen regulation in intercropped wheat/faba beans can control powdery mildew and stripe rust, and optimize wheat yield. Intercropping at 180 kg ha-1 N2 resulted in the highest yield.

Precision Targeting of pten-Null Triple-Negative Breast Tumors Guided by Electrophilic Metabolite Sensing.

Off-target effects continue to impede disease interventions, particularly when targeting a specific protein within a family of similar proteins, such as kinase isoforms that play tumor-subtype-specific roles in cancers. Exploiting the specific electrophilic-metabolite-sensing capability of Akt3, versus moderate or no sensing, respectively, by Akt2 and Akt1, we describe a first-in-class functionally Akt3-selective covalent inhibitor [MK-H(F)NE], wherein the electrophilic core is derived from the native reactive lipid metabolite HNE. Mechanistic profiling and pathway interrogations point to retention of the metabolite's structure-as opposed to implicit electrophilicity-as being essential for biasing isoform preference, which we found translates to tumor-subtype specificity against pten-null triple-negative breast cancers (TNBCs). MK-H(F)NE further enables novel downstream target identification specific to Akt3-function in disease. In TNBC xenografts, MK-H(F)NE fares better than reversible pan-Akt-inhibitors and does not show commonly observed side-effects associated with Akt1-inhibition. Inhibitors derived from native-metabolite sensing are thus an enabling plan-of-action for unmasking kinase-isoform-biased molecular targets and tumor-subtype-specific interventions.

Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic.

Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development.