A simple and general method is presented herein for the in situ preparations of circularly polarized luminescence (CPL)‐active microcrystals with a large luminescence dissymmetry factor glum, high ...fluorescence quantum efficiency (ΦFL), wide emission color tenability, and well‐ordered morphology. The reactions of pyridine‐containing achiral molecules 1–7 with chiral camphor sulfonic acid ((±)‐CSA) gave crystalline microplates formed by hydrogen bonding interactions between the protonated pyridinium units and the sulfonic anions. The chiral information of CSA are effectively transferred to the microcrystals by hydrogen bonding to afford full‐color CPL from deep‐blue to red with glum in the order of 10−2 and ΦFL up to 80 %. Moreover, organic microcrystals with high‐performance white CPL (ΦFL=46 %; |glum|=0.025) are achieved via the light‐harvesting energy transfer between blue and yellow emitters.
As a result of the efficient hydrogen‐bonding‐mediated chirality transfer and light‐harvesting energy transfer, well‐ordered ionic microcrystals formed between pyridine‐containing achiral molecules and chiral camphor sulfonic acid display full‐color and homogeneously white circularly polarized luminescence (CPL) with ΦFL of up to 80 % and glum in the order of 10−2.
The radical-involved 1,2-difunctionalization of alkenes has developed into a robust tool for preparation of complex organic molecules. Despite significant advances in this area, the catalytic ...asymmetric version still remains a challenging task mainly due to the difficulty in the stereocontrol of the highly reactive radical intermediates. Recently, owing to the good single-electron transfer ability and coordination with chiral ligands of copper catalysts, remarkable achievements in radical-involved asymmetric alkene difunctionalization have been made
via
synergistic combination of copper and chiral ligands. This tutorial review highlights the recent progress in copper-catalysed radical-involved asymmetric 1,2-difunctionalization of alkenes and the mechanistic scenarios governing the stereocontrol, with an emphasis on utilization of chiral ligands.
This tutorial review highlights the recent progress in copper-catalysed radical asymmetric 1,2-difunctionalization of alkenes.
A
bstract
We consider the continuum limit of 4d planar fishnet diagrams using integrable spin chain methods borrowed from the
N
= 4 Super-Yang-Mills theory. These techniques give us control on the ...scaling dimensions of single-trace operators for all values of the coupling constant in the fishnet theory. We use them to study the thermodynamical limit of the BMN operator corresponding to the spin chain ferromagnetic vacuum. We find that its scaling dimension exhibits a critical behaviour when the coupling constant approaches Zamolodchikov’s critical coupling. Analysis close to that point suggests that the continuum limit of the fishnet graphs is controlled by the two-dimensional
AdS
5
non-linear sigma model. More generally, we present evidence that the fishnet diagrams define an integrable lattice regularization of the
AdS
5
model. A system of massless TBA equations is derived for the tachyon energy by dualizing the TBA equations of the weakly coupled planar
N
= 4 SYM theory.
Recently, with the boosted development of radical chemistry, enantioselective functionalization of C(sp
)-H bonds via a radical pathway has witnessed a renaissance. In principle, two distinct ...catalytic modes, distinguished by the steps in which the stereochemistry is determined (the radical formation step or the radical functionalization step), can be devised. This Perspective discusses the state-of-the-art in the area of catalytic enantioselective C(sp
)-H functionalization involving radical intermediates as well as future challenges and opportunities.
Nitrogen is the main limiting nutrient after carbon, hydrogen and oxygen for photosynthetic process, phyto-hormonal, proteomic changes and growth-development of plants to complete its lifecycle. ...Excessive and inefficient use of N fertilizer results in enhanced crop production costs and atmospheric pollution. Atmospheric nitrogen (71%) in the molecular form is not available for the plants. For world's sustainable food production and atmospheric benefits, there is an urgent need to up-grade nitrogen use efficiency in agricultural farming system. The nitrogen use efficiency is the product of nitrogen uptake efficiency and nitrogen utilization efficiency, it varies from 30.2 to 53.2%. Nitrogen losses are too high, due to excess amount, low plant population, poor application methods etc., which can go up to 70% of total available nitrogen. These losses can be minimized up to 15-30% by adopting improved agronomic approaches such as optimal dosage of nitrogen, application of N by using canopy sensors, maintaining plant population, drip fertigation and legume based intercropping. A few transgenic studies have shown improvement in nitrogen uptake and even increase in biomass. Nitrate reductase, nitrite reductase, glutamine synthetase, glutamine oxoglutarate aminotransferase and asparagine synthetase enzyme have a great role in nitrogen metabolism. However, further studies on carbon-nitrogen metabolism and molecular changes at omic levels are required by using "whole genome sequencing technology" to improve nitrogen use efficiency. This review focus on nitrogen use efficiency that is the major concern of modern days to save economic resources without sacrificing farm yield as well as safety of global environment, i.e. greenhouse gas emissions, ammonium volatilization and nitrate leaching.
Circularly polarized luminescence (CPL)‐active molecular materials have drawn increasing attention due to their promising applications for next‐generation display and optoelectronic technologies. ...Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor (glum) and high quantum yield (Φ). A pair of enantiomeric N N C‐type Pt(II) complexes (L/D)‐1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL‐inactive, the spin‐coated thin films of (L/D)‐1 exhibit giantly‐amplified circularly polarized phosphorescences with |glum| of 0.53 at 560 nm and Φair of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor |gabs| of 0.37–0.43 at 480 nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes (L/D)‐2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of (L/D)‐1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of (L/D)‐1 in CPL‐contrast imaging and inducing CP light generation from achiral emitters and common light‐emitting diode lamps have been successfully realized.
The thin films of chiral Pt(II) complexes exhibit giantly‐amplified circularly polarized luminescence (CPL) with |glum| of 0.53 at 560 nm and Φ of ~50 % in air, as a result of the hierarchical formation of crystalline fibrillar networks upon spin coating. These films display promising potentials in CPL‐contrast imaging and inducing circularly polarized light generation from achiral emitters and common LED lamps.
Fibroblast growth factor 21 (FGF21), a known risk factor for atherosclerosis, is readily regulated by exercise, and it can inhibit NOD-like receptor protein 3 (NLRP3)-mediated pyroptosis. However, it ...is not clear whether aerobic exercise inhibits atherosclerosis via these pathways. Eight-week-old apolipoprotein E-deficient (ApoE.sup.-/-) mice on a high-fat diet were randomly divided into 1-h post-exercise (EX-1h), 24-h post-exercise (EX-24h), and sedentary (SED) groups. C57BL/6J wild-type mice fed normal chow served as controls (WT group). Mice in the EX-1h and EX-24h groups were subjected to treadmill exercise training for 12 weeks. Aerobic exercise reduced body weight; blood glucose, lipid, and inflammation levels; and aortic plaque area proportion. Aerobic exercise increased the sensitivity of FGF21 by upregulating the expression of the downstream receptor adiponectin (ApN); the serum FGF21 level after exercise increased initially, and then decreased. Aerobic exercise downregulated the expression of NLRP3 inflammasome-mediated pyroptosis-related markers in the aorta, and FGF21 may participate in the above process. Meanwhile, the liver may be the tissue source of serum FGF21 during aerobic exercise. In conclusion, aerobic exercise may inhibit atherogenesis by regulating FGF21 and NLRP3 inflammasome-mediated pyroptosis. Our study provides new information on the atherosclerosis-preventing mechanism of aerobic exercise.
Conventional square‐planar platinum complexes typically form one‐dimensional assemblies as a result of unidirectional metallophilic and/or π⋅⋅⋅π intermolecular interactions. Organoplatinum(II) ...complexes with a cruciform shape are presented herein to construct two‐dimensional (2D) microcrystals with full‐color and white phosphorescence. These 2D crystals show unique monocomponent π⋅⋅⋅π stacking, from either the cyclometalating or noncyclometalating ligand, and the bicomponent alternate π⋅⋅⋅π stacking from both ligands along different facet directions. Anisotropic tri‐directional waveguiding is further implemented on a single hexagonal microcrystal. These results demonstrate the great capability of the organoplatinum(II) cruciform as a general platform to fabricate 2D phosphorescent micro‐/nanocrystals for advanced photonic applications.
The controllable preparations of two‐dimensional phosphorescent crystals remain a challenging task. In stark contrast to the conventional one‐dimensional assemblies of square‐planar platinum complexes, organoplatinum(II) complexes with a cruciform shape form two‐dimensional microcrystals with full‐color and white phosphorescence by unique molecular stackings, opening a new avenue for the preparations of phosphorescent micro/nanostructures for advanced photonic applications.
The development of circularly polarized electroluminescence (CPEL) is currently hampered by the high difficulty and cost in the syntheses of suitable chiral materials and the notorious chirality ...diminishment issue in electrical devices. Herein, diastereomeric IrIII and RuII complexes with chiral (±)‐camphorsulfonate counteranions are readily synthesized and used as the active materials in circularly polarized light‐emitting electrochemical cells to generate promising CPELs. The addition of the chiral ionic liquid (±)‐1‐butyl‐3‐methylimidazole camphorsulfonate into the active layer significantly improves the device performance and the electroluminescence dissymmetry factors (≈10−3), in stark contrast to the very weak circularly polarized photoluminescence of the spin‐coated films of these diastereomeric complexes. Control experiments with enantiopure IrIII complexes suggest that the chiral anions play a dominant role in the electrically‐induced amplification of CPELs.
By using a chiral anion strategy, electrically amplified circularly polarized luminescence (CPL) is realized in light‐emitting electrochemical cells of readily obtained diastereomeric ionic transition‐metal complexes. The addition of a chiral ionic liquid (IL) into the active layer significantly improves the device performance and the electroluminescence dissymmetry factors.
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