Optimizing Agronomic Management Practices for Enhanced Radiation Capture and Improved Radiation Use Efficiency in Winter Wheat.

Increased aboveground biomass is contingent on enhanced photosynthetically active radiation intercepted by the canopy (IPAR), improved radiation use efficiency (RUE), or both. We investigated whether and how optimized agronomic management practices promote IPAR and RUE. Four integrated agronomic management treatments, i.e., local traditional practice (LP), improved local traditional practice (ILP), high-yield agronomic management (HY), and improved high-yield agronomic management (IHY), were compared over two wheat (Triticum aestivum L.) growing seasons. The average grain yield obtained with IHY was 96% relative to that of HY and was 7% and 23% higher than that with ILP and LP, respectively. Both HY and IHY consistently supported large values of the leaf area index and IPAR fraction, thereby increasing total IPAR. Treatment HY showed increased pre-anthesis RUE, manifested as a higher specific leaf nitrogen content and whole-plant N nutrition index at anthesis. The highest pre-anthesis aboveground biomass was obtained with HY due to the highest pre-anthesis IPAR and RUE. Along with a higher canopy apparent photosynthetic rate, IHY produced higher post-anthesis aboveground biomass due to its higher post-anthesis IPAR and RUE. Treatment IHY had a slightly lower total IPAR but a similar total RUE and harvest index, thus producing a slightly lower grain yield relative to HY. These results demonstrate that the optimized agronomic management practice used under IHY effectively enhances radiation capture and improves radiation utilization. Additionally, the net profit for IHY was higher than that for HY, ILP, and LP by 8%, 11%, and 88%, respectively. Considering the high grain yield, high RUE and high economic benefits, we recommend IHY as the agronomic management practice in the target region, although further study of improvements in pre-anthesis RUE is required.

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes.

We have established an efficient ruthenium(II) and iodine anion cocatalyzed dihalogenation and cascade cyclization of internal alkyne-tethered cyclohexadienones, which stereoselectively afforded numerous dihalogenation products with a bioactive hydrobenzofuran skeleton in high yields under mild conditions. In this transformation, the reaction pathway was determined by the concentration of electrophilic iodine reagent, which also provided a strategy for control of the reaction selectivity. Furthermore, this method features the use of 1,2-dihaloroethane as the halogen source via iodine anion catalyst.

Construction of C-P Bonds from Free Cyclobutanone Oximes and Chlorophosphines via Radical-Radical Coupling.

Herein, we report a catalyst-free reaction of cyclobutanone oximes with chlorophosphines (R2PCl), which forms a fragile C═N-O-PR2 species that undergoes N-O homolysis, fragmentation, and radical-radical coupling, leading to the formation of cyano-containing phosphine oxides in good yields. The reaction features an in situ activation of cyclobutanone oximes for radical generation, in which R2PCl plays a dual role as both an activator and a reactant.

Enzyme-triggered on-demand release of a H2O2-self-supplying CuO2@Fe3O4 nanoagent for enhanced chemodyamic antimicrobial therapy and wound healing.

Nanoagents for chemodynamic therapy (CDT) hold a promising future in the field of antimicrobials, especially copper peroxide (CuO2) (CP) nanomaterials which have garnered significant attention due to their ability to self-supply H2O2. Nevertheless, the poor stability of CuO2 remains a critical challenge which restricts its practical application in the antibacterial field. In this study, an advanced nano-antimicrobial system HA-CP@Fe3O4 with enzyme-responsive properties is developed by coating hyaluronic acid (HA) on CuO2-loaded iron tetraoxide nanoparticles. The coating of HA not only stabilizes the CuO2 nanomaterials but also provides responsiveness towards the enzyme hyaluronidase, which is typically secreted by some bacteria. The outer layer of HA in HA-CP@Fe3O4 undergoes decomposition in the presence of hyaluronidase-secreting bacteria, resulting in the release of CuO2@Fe3O4. The released CuO2@Fe3O4 then self-supplies H2O2 and generates reactive oxygen species (ROS) within the infected microenvironment through Fenton and Russell effects, to ultimately achieve effective and precise antimicrobial activity. Simultaneously, the magnetic property provided by Fe3O4 allows the substance to be directed towards the infection site. Both in vitro and in vivo tests demonstrated that HA-CP@Fe3O4 exhibited excellent antimicrobial capabilities at low concentration (30 µg mL-1), exceptional biocompatibility and the ability to accelerate wound healing. The findings of this work offer a new and promising approach for targeted and precise CDT.

Recent Advances of Chiral Isolated and Small Organic Molecules: Structure and Properties for Circularly Polarized Luminescence.

This paper explores recent advancements in the field of circularly polarized luminescence (CPL) exhibited by small and isolated organic molecules. The development and application of small CPL molecule are systematically reviewed through eight different chiral skeleton sections. Investigating the intricate interplay between molecular structure and CPL properties, the paper aims at providing and enlighting novel strategies for CPL-based applications.

Nitroalkanes as thioacyl equivalents to access thioamides and thiopeptides.

Thioamides are an important, but a largely underexplored class of amide bioisostere in peptides. Replacement of oxoamide units with thioamides in peptide therapeutics is a valuable tactic to improve biological activity and resistance to enzymatic hydrolysis. This tactic, however, has been hampered by insufficient methods to introduce thioamide bonds into peptide or protein backbones in a site-specific and stereo-retentive fashion. In this work, we developed an efficient and mild thioacylation method to react nitroalkanes with amines directly in the presence of elemental sulfur and sodium sulfide to form a diverse range of thioamides in high yields. Notably, this convenient method can be employed for the controlled thioamide coupling of multifunctionalized peptides without epimerization of stereocenters, including the late stage thioacylation of advanced compounds of biological and medicinal interest. Experimental interrogation of postulated mechanisms currently supports the intermediacy of thioacyl species.

Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes.

Hepta-2,3,5-trienedioates 1 have been employed as substrates to explore Lewis base-catalyzed annulation reactions. This leads to the discovery of a phosphine-catalyzed [3+2] annulation of 1 with electron-deficient alkenes for the construction of exocyclic olefinic cyclopentenes in good yields and moderate E:Z ratios under mild conditions. The annulation is believed to proceed in a tandem [3+2] cyclization and double bond migration in which the ε-ester is crucial to both processes. This reaction also showcases a substrate-controlled divergent reactivity compared to that of a previous report.

Optimized management strategy increased grain yield, promoted nitrogen balance, and improved water productivity in winter wheat.

The increasing costs of agricultural production and environmental concerns reinforce the need to reduce resource inputs. Improvements in nitrogen (N) use efficiency (NUE) and water productivity (WP) are critical for sustainable agriculture. We aimed to optimize management strategy to increase wheat grain yield, promote N balance, and improve NUE and WP. A 3-year experiment was conducted with four integrated treatments: conventional practice treatment (CP); improvement of conventional practice treatment (ICP); high-yield management treatment (HY), which aimed for maximizing grain yield regardless of resource inputs cost; and integrated soil and crop system management treatment (ISM), which aimed for testing an optimal combination of sowing date, seeding rate, and fertilization and irrigation management. The average grain yield for ISM was 95.86% of that for HY and was 5.99% and 21.72% higher than that for ICP and CP, respectively. ISM promoted N balance as relatively higher aboveground N uptake, lower inorganic N residue, and lowest inorganic N loss. The average NUE for ISM was 4.15% lower than that for ICP and was remarkably higher than that for HY and CP by 26.36% and 52.37%, respectively. The increased soil water consumption under ISM was mainly due to its increased root length density. Along with a high level of grain yield, ISM obtained a relatively adequate water supply due to the effective use of soil water storage, thereby increasing the average WP by 3.63%-38.10% in comparison with other integrated management treatments. These results demonstrated that optimized management strategy (appropriately delaying sowing date, increasing seeding rate, and optimizing fertilization and irrigation management) used under ISM could promote N balance and improve WP while increasing grain yield and NUE in winter wheat. Therefore, ISM can be considered a recommendable management strategy in the target region.

Phosphine-Catalyzed Stereoselective Ring-Opening Addition of Cyclopropenones with Nucleophiles.

A phosphine-catalyzed ring-opening addition reaction of cyclopropenones with a variety of nucleophiles (NuH), including oxygen-, nitrogen-, sulfur-, and carbon-based ones, has been investigated, which produces potentially useful α,ß-unsaturated carbonyl derivatives in high yields (up to 99%), high regioselectivity, and exclusive E-selectivity. The reaction proceeds in high efficiency under very mild conditions using only 1 mol % PPh3 as the catalyst at room temperature. The method is also amenable for the synthesis of deuterated alkenes when deuterated nucleophiles (NuD) are employed. The mechanism is investigated by experiments and DFT calculations, which suggests an α-ketenyl phosphorus ylide as a key intermediate in the catalytic cycle that captures the nucleophiles in a stereoselective manner.

Iodine Anion Catalyzed Cross-Dehydrogenative Aromatization for Access to Aromatic Amines.

A highly efficient iodine anion catalyzed cross-dehydrogenative aromatization of cyclohexenones with amines has been developed under metal-free conditions, which affords aromatic amines in good to excellent yields with a broad substrate scope. Meanwhile, this reaction provides a new method for the construction of C(sp2)-N bonds and also a new strategy for slow generation of oxidants or electrophiles via in situ dehalogenation. Moreover, this protocol affords a rapid and concise approach to chiral NOBIN derivatives.

Synthesis of Phosphinic Amides from Chlorophosphines and Hydroxyl Amines via P(III) to P(V) Rearrangement.

Phosphoranyl radicals are essential mediators to bring about new radicals but often produce a stoichiometric amount of phosphine oxide/sulfide waste. Herein, we devised a phosphorus-containing species as a radical precursor, but without the generation of phosphorus waste. Accordingly, a catalyst-free synthesis of phosphinic amides from hydroxyl amines and chlorophosphines via P(III) to P(V) rearrangement is described. Mechanistically, it may involve the initial formation of a R2N-O-PR2 species that undergoes homolysis of N-O bonds and subsequent radical recombination.

Two-in-one platform based on conjugated polymer for ultrasensitive ratiometric detection and efficient removal of perfluoroalkyl substances from environmental water.

Continuous emergence of persistent organic pollutants perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in various water bodies around the world poses a serious threat to the global ecosystem. The exploration of advanced detection/removal techniques to monitor/treat such type of toxicants is urgently required. Herein, we unveiled a donor-acceptor type conjugated polymer PF-DBT-Im as a first-of-its-kind ratiometric fluorescent probe for visual, amplified, and specific monitoring of PFOA and PFOS with ultra-low detection limits of 6.12 nM (PFOA) and 14.3 nM (PFOS), respectively. PF-DBT-Im undergoes strong aggregation after binding with PFOA/PFOS as evident by transmission electron microscopy, zeta potential measurements, and dynamic light scattering studies. This promotes interchain Förster resonance energy transfer process to endorse an obvious emission color change from blue-to-magenta under ultraviolet lamp excitation. Consequently, a smartphone-integrated portable device is fabricated for realizing rapid and on-site detection of PFOA/PFOS. Besides, a new class of magnetic adsorbent Fe3O4@NH2&F13 is also prepared and used in combination with PF-DBT-Im to remove PFOA/PFOS from the environmental water effectively and rapidly as confirmed by liquid chromatography-mass spectrometry analysis. Thus, utilizing the excellent signal amplification property of PF-DBT-Im and the remarkable magnetic separation capability of Fe3O4@NH2&F13, a multifunctional system is developed for step-wise recognition and separation of PFOA/PFOS from the environmental water proficiently and rapidly.

Phosphine-catalyzed activation of cyclopropenones: a versatile C3 synthon for (3+2) annulations with unsaturated electrophiles.

We herein report a phosphine-catalyzed (3 + 2) annulation of cyclopropenones with a wide variety of electrophilic π systems, including aldehydes, ketoesters, imines, isocyanates, and carbodiimides, offering products of butenolides, butyrolactams, maleimides, and iminomaleimides, respectively, in high yields with broad substrate scope. An α-ketenyl phosphorous ylide is validated as the key intermediate, which undergoes preferential catalytic cyclization with aldehydes rather than stoichiometric Wittig olefinations. This phosphine-catalyzed activation of cyclopropenones thus supplies a versatile C3 synthon for formal cycloadditon reactions.

DABCO-Catalyzed [4 + 2] Annulation of 5-Methylenehex-2-ynedioates with Electron-Deficient Alkenes.

Herein, we describe a DABCO-catalyzed [4 + 2] annulation between 5-methylenehex-2-ynedioates and electron-deficient olefins to afford functionalized cyclohexadienes in good yields under mild conditions. The use of ß- and ε-carbons of the substrates for C-C bond formation is distinct from previous reports showing a substrate-controlled divergent reactivity. The annulation is believed to proceed in domino cyclization initiated by a cross Rauhut-Currier reaction.

Ru(II)-Catalyzed Difunctional Pyridyloxy-Directed Regio- and Stereospecific Addition of Carboxylic Acids to Internal Alkynes.

A highly efficient Ru(II)-catalyzed regio- and stereospecific hydro-oxycarbonylation of unsymmetrical internal alkynes bearing a difunctional 2-pyridyloxy directing group with carboxylic acids has been developed, which provides allylic (Z)-enol esters in good to excellent yields with a broad substrate scope under mild conditions. The difunctional directing group can be diversely derivatized, particularly undergoing allylic substitution with various nucleophiles to afford ß-functionalized (Z)-enol esters without directing groups.

Rapid Construction of Hexacyclic Indolines via the Ru(II)-Catalyzed C-H Activation Initiated Cascade Cyclization of Phenidones with Enynones.

A highly efficient cascade cyclization of phenidones and enynones has been developed via a Ru(II)-catalyzed C-H activation initiated indole formation/Diels-Alder reaction/iminium ion cyclization sequence, which afforded hexacyclic indolines as single diastereomer in good to excellent yields with a broad substrate scope under mild conditions. The reaction features the simultaneous generation of five new chemical bonds and four new rings in one pot, providing a rapid and concise approach toward polycyclic indoline alkaloids and their analogues.

Phosphine-Catalyzed Internal Redox [4 + 2] Annulation between 1,4-Enynoates and Electron-Deficient Alkenes.

Herein we describe a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, in which the γ- and φ-C(sp3)-H of the enynoates are formally oxidized for the annulation while the alkynyl moiety is converted to an alkene. The reaction offers an efficient synthesis of highly functionalized cyclohexenes in moderate to good yields with exclusive regioselectivity and high diastereoselectivity under mild conditions.

Synthesis of Indole-Fused Oxepines via C-H Activation Initiated Diastereoselective [5 + 2] Annulation of Indoles with 1,6-Enynes.

A rhodium-catalyzed diastereoselective formal [5 + 2] annulation of indoles with cyclohexadienone-containing 1,6-enynes has been established via indole 2,3-difunctionalization. The reaction, probably proceeding through tandem indole C2-H alkenylation and intramolecular Friedel-Crafts alkylation relay, provides rapid construction of indole-fused oxepines in good to excellent yields with a broad substrate scope. This method also features concomitant construction of cis-hydrobenzo[b] oxepine scaffolds, a core unit found in numerous natural products of important biological activities.

Catalyst-Free [3 + 3] Annulation/Oxidation of Cyclic Amidines with Activated Olefins: When the Substrate Olefin Is Also an Oxidant.

Herein we describe a catalyst-free regioselective [3 + 3] annulation/oxidation reaction of cyclic amidines such as DBU (1,8-diazabicyclo(5.4.0)undec-7-ene) and DBN (1,5-diazabicyclo(4.3.0)non-5-ene) with activated olefins, i.e., 2-arylidenemalononitriles and 2-cyano-3-aryl acrylates, to afford tricyclic 2-pyridones and pyridin-2(1H)-imines, respectively. The mechanism has been proposed based on DFT calculations. In the reaction, the cyclic amidines serve as C,N-bisnucleophiles for the cyclization, while the olefins play a dual role by acting as both reactants and oxidants.

Phosphine-Catalyzed Cross-Coupling of Benzyl Halides and Fumarates.

A phosphine-catalyzed olefinic cross-coupling between benzyl halides and fumarates is described, which affords trisubstituted alkenes in good yields and excellent E-selectivity under metal-free conditions. Mechanistic studies suggest a catalytic cycle involving phosphorus ylide formation, Michael addition, water-assisted hydrogen transfer, and phosphine elimination.