Optimal Fertilizer Application Reduced Nitrogen Leaching and Maintained High Yield in Wheat-Maize Cropping System in North China.

Agricultural nitrogen (N) non-point source pollution in the North China Plain is a major factor that affects water quality and human health. The characteristics of N leaching under different N application conditions should be further quantified accurately in winter wheat (Triticum aestivum L.) and summer maize (Zea mays L.) rotation farmland in North China, and a basis for reducing the risk and evaluation of N leaching in this area. A three-year field experiment was conducted using an in situ leakage pond method at a typical farmland in Henan in 2017-2020. Crop yield, soil nitrate N residues, and N utilization were also studied during the study period. Five N fertilizer rates were established with 0 (CK), 285 (LN), 465 (MN), 510 (MNO), and 645 (HN) kg N ha-1 for one rotation cycle. MNO was applied with chemical and organic fertilizers. The concentration of nitrate N in the soil leaching solution of CK, LN, MN, MNO, and HN was 0.81-, 1.49-, 3.65-, 5.55-, and 7.57-fold that of the World Health Organization's standard for underground drinking water. The exponential relationship between the N application rate and leaching was obtained when the annual N input exceeded 300 kg ha-1, and the N leaching rate increased greatly. The leaching rate of nitrate N in the total N was 50.6-82.4% under different treatments of N application. The combination of chemical and organic fertilizers treatment (MNO) reduced the amount of N that was leached in dry years. The nitrate leaching amount of summer maize accounts for 83.0%, 49.4%, and 72.0% of the total nitrate leaching amount of the whole rotation cycles in 2017-2020. LN and MN were recommended as the optimized N application here (285-465 kg N ha-1) with the two-season rotation grain yield of 17.2 ton ha-1 (16.5-17.9 ton ha-1) and nitrate N leaching of 21.6 kg ha-1 (12.6-30.5 kg ha-1).

Ynonylation of Acyl Radicals by Electroinduced Homolysis of 4-Acyl-1,4-dihydropyridines.

Herein we report the conversion of 4-acyl-1,4-dihydropyridines (DHPs) into ynones under electrochemical conditions. The reaction proceeds via the homolysis of acyl-DHP under electron activation. The resulting acyl radicals react with hypervalent iodine(III) reagents to form the target ynones or ynamides in acceptable yields. This mild reaction condition allows wider functionality tolerance that includes halides, carboxylates, or alkenes. The synthetic utility of this methodology is further demonstrated by the late-stage modification of complex molecules.

Synthetic Homogeneous Glycoforms of the SARS-CoV-2 Spike Receptor-Binding Domain Reveals Different Binding Profiles of Monoclonal Antibodies.

SARS-CoV-2 attaches to its host receptor, angiotensin-converting enzyme 2 (ACE2), via the receptor-binding domain (RBD) of the spike protein. The RBD glycoprotein is a critical target for the development of neutralizing antibodies and vaccines against SARS-CoV-2. However, the high heterogeneity of RBD glycoforms may lead to an incomplete neutralization effect and impact the immunogenic integrity of RBD-based vaccines. Investigating the role of different carbohydrate domains is of paramount importance. Unfortunately, there is no viable method for preparing RBD glycoproteins with structurally defined glycans. Herein we describe a highly efficient and scalable strategy for the preparation of six glycosylated RBDs bearing defined structure glycoforms at T323, N331, and N343. A combination of modern oligosaccharide, peptide synthesis and recombinant protein engineering provides a robust route to decipher carbohydrate structure-function relationships.

Changes of nitrogen deposition in China from 1980 to 2018.

China has experienced a dramatic change in atmospheric reactive nitrogen (Nr) emissions over the past four decades. However, it remains unclear how nitrogen (N) deposition has responded to increases and/or decreases in Nr emissions. This study quantitatively assesses temporal and spatial variations in measurements of bulk and calculated dry N deposition in China from 1980 to 2018. A long-term database (1980-2018) shows that bulk N deposition peaked in around 2000, and had declined by 45% by 2016-2018. Recent bulk and dry N deposition (based on monitoring from 2011 to 2018) decreased from 2011 to 2018, with current average values of 19.4 ± 0.8 and 20.6 ± 0.4 kg N ha-1 yr-1, respectively. Oxidized N deposition, especially dry deposition, decreased after 2010 due to NOx emission controls. In contrast, reduced N deposition was approximately constant, with reductions in bulk NH4+-N deposition offset by a continuous increase in dry NH3 deposition. Elevated NH3 concentrations were found at nationwide monitoring sites even at urban sites, suggesting a strong influence of both agricultural and non-agricultural sources. Current emission controls are reducing Nr emissions and deposition but further mitigation measures are needed, especially of NH3, built on broader regional emission control strategies.

Catalyst-Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro-Induced Radical Formation.

Electro-induced reduction of redox active esters and N-phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron-poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst-free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.

Histidine-Specific Peptide Modification via Visible-Light-Promoted C-H Alkylation.

Histidine (His) carries a unique heteroaromatic imidazole side chain and plays irreplaceable functional roles in peptides and proteins. Existing strategies for site-selective histidine modification predominantly rely on the N-substitution reactions of the moderately nucleophilic imidazole group, which inherently suffers from the interferences from lysine and cysteine residues. Chemoselective modification of histidine remains one of the most difficult challenges in peptide chemistry. Herein, we report peptide modification via radical-mediated chemoselective C-H alkylation of histidine using C4-alkyl-1,4-dihydropyridine (DHP) reagents under visible-light-promoted conditions. The method exploits the electrophilic reactivity of the imidazole ring via a Minisci-type reaction pathway. This method exhibits an exceptionally broad scope for both peptides and DHP alkylation reagents. Its utility has been demonstrated in a series of important peptide drugs, complex natural products, and a small protein. Distinct from N-substitution reactions, the unsubstituted nitrogen groups of the modified imidazole ring are conserved in the C-H alkylated products.

Funneled potential and flux landscapes dictate the stabilities of both the states and the flow: Fission yeast cell cycle.

Using fission yeast cell cycle as an example, we uncovered that the non-equilibrium network dynamics and global properties are determined by two essential features: the potential landscape and the flux landscape. These two landscapes can be quantified through the decomposition of the dynamics into the detailed balance preserving part and detailed balance breaking non-equilibrium part. While the funneled potential landscape is often crucial for the stability of the single attractor networks, we have uncovered that the funneled flux landscape is crucial for the emergence and maintenance of the stable limit cycle oscillation flow. This provides a new interpretation of the origin for the limit cycle oscillations: There are many cycles and loops existed flowing through the state space and forming the flux landscapes, each cycle with a probability flux going through the loop. The limit cycle emerges when a loop stands out and carries significantly more probability flux than other loops. We explore how robustness ratio (RR) as the gap or steepness versus averaged variations or roughness of the landscape, quantifying the degrees of the funneling of the underlying potential and flux landscapes. We state that these two landscapes complement each other with one crucial for stabilities of states on the cycle and the other crucial for the stability of the flow along the cycle. The flux is directly related to the speed of the cell cycle. This allows us to identify the key factors and structure elements of the networks in determining the stability, speed and robustness of the fission yeast cell cycle oscillations. We see that the non-equilibriumness characterized by the degree of detailed balance breaking from the energy pump quantified by the flux is the cause of the energy dissipation for initiating and sustaining the replications essential for the origin and evolution of life. Regulating the cell cycle speed is crucial for designing the prevention and curing strategy of cancer.

TMSOTf mediated stereoselective synthesis of α-C-glycosides from unactivated aryl acetylenes.

A metal free and highly stereoselective procedure for the synthesis of 2,3-unsaturated-C-glycosides has been developed between glycals and unactivated aryl acetylenes in the presence of TMSOTf through a triflated C-vinyl glycosides intermediate. The flexibility of the procedure was tested by a wide variety of glycals and unactivated aryl acetylenes (20 examples). The corresponding alkynyl C-glycosides were obtained in good yields with completely α-selectivity in a short time (<25 min). And a plausible mechanism for the synthesis of alkynyl C-glycosides was depicted.

An efficient method for the synthesis of pyranoid glycals.

A simple and efficient procedure was designed for the preparation of pyranoid glycals. In a novel fashion, a series of protected glycopyranosyl bromides underwent reductive elimination in the presence of zinc dust and ammonium chloride in CH3CN at 30-60 °C. The corresponding glycals were obtained with excellent isolated yields (72-96%) in a short time (20-50 min). Furthermore, the transformation was compatible with different protection patterns and conveniently scalable (86% for 45 g acetobromoglucose) which made it very applicable in organic synthesis.

High nitrogen deposition in an agricultural ecosystem of Shaanxi, China.

Atmospheric nitrogen (N) deposition plays an important role in the global N cycle. Data for dry and wet N deposition in agricultural ecosystem of Shaanxi in China is still imperfect; in this study, we continuously measured concentrations and fluxes of dry N deposition from 2010 to 2013 in Yangling district of Shaanxi province and wet N deposition from 2010 to 2012. The average annual concentrations of NH3, NO2, HNO3, particulate ammonium, and nitrate (pNH4 (+) and pNO3 (-)) varied among 3.9-9.1, 6.6-8.0, 1.2-1.4, 3.1-4.3, and 3.3-4.8 µg N m(-3), respectively, with mean values of 6.0, 7.2, 1.3, 3.8, and 4.1 µg N m(-3), respectively, during the entire monitoring period. The annual NH4 (+)-N and NO3 (-)-N concentrations in precipitation ranged 3.9-4.3 and 2.8-3.4 mg N L(-1) with the mean values of 4.1 and 3.3 mg N L(-1). The NH4 (+)-N/NO3 (-)-N ratio in rainfall averaged 1.2. Dry N deposition flux was determined to be 19.2 kg N ha(-1) year(-1) and the wet N deposition flux was 27.2 kg N ha(-1) year(-1). The amount of total atmospheric N deposition (dry plus wet) reached 46.4 kg N ha(-1) year(-1), in which dry deposition accounted 41 %. Gaseous N deposition comprised over 75 % of the dry deposition, and the proportion of oxidized N in dry deposition was equal to the reduced N. Therefore, the results suggest that more stringent regional air pollution control policies are required in the target area and that N deposition is an important nutrient resource from the atmosphere that must be taken into consideration in nutrient management planning of agricultural ecosystems.

Facile TMSOTf-catalyzed preparation of 2-deoxy α-O-aryl-D-glycosides from glycosyl acetates.

2-Deoxy α-O-aryl glycosides were conveniently obtained by reaction of 2-deoxy-glycosyl acetates with phenols in the presence of TMSOTf as the promoter. The current method provides the O-aryl glycosides with good to excellent yields, and sole alpha selectivity.