A new diterpenoid alkaloid from Aconitum hemsleyanum

Abstract

A new C₁₉-diterpenoid alkaloid named hemsleyaline (1), along with fourteen known alkaloids (2-15), were isolated from the roots of Aconitum hemsleyanum Pritz. (Ranunculaceae), a herbal medicine in southwest China. Their structures were established on the basis of extensive spectroscopic analyses. Compound 1 showed mild cholinesterase inhibitory effect with IC₅₀ value of 471?±?9?μM.     

Bridge Bonded Oxygen Ligands between Approximated FeN4 Sites Confer Catalysts with High ORR Performance

The applications of the most promising Fe—N–C catalysts are prohibited by their limited intrinsic activities. Manipulating the Fe energy level through anchoring electron‐withdrawing ligands is found effective in boosting the catalytic performance. However, such regulation remains elusive as the ligands are only uncontrollably introduced oweing to their energetically unstable nature. Herein, we report a rational manipulation strategy for introducing axial bonded O to the Fe sites, attained through hexa‐coordinating Fe with oxygen functional groups in the precursor. Moreover, the O modifier is stabilized by forming the Fe?O?Fe bridge bond, with the approximation of two FeN₄ sites. The energy level modulation thus created confers the sites with an intrinsic activity that is over 10 times higher than that of the normal FeN₄ site. Our finding opens a novel strategy to manage coordination environments at an atomic level for high activity ORR catalysts.     

High‐Tc Enantiomeric Ferroelectrics Based on Homochiral Dabco‐derivatives (Dabco=1,4‐Diazabicyclo[2.2.2]octane)

1,4‐Diazabicyclo[2.2.2]octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the [H₂dabco]²⁺ in the non‐ferroelectric [H₂dabco][TFSA]₂ (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics [R and S‐2‐Me‐H₂dabco][TFSA]₂. The two enantiomers show two sequential phase transitions with transition temperature (T_c) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, [R and S‐2‐Me‐H₂dabco][TFSA]₂ are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics.     

Crystallization Mechanism of 9,9-Diphenyl-dibenzosilole from Solids

Organic semiconductor (OSC) crystals have great potential to be applied in many fields, as they can be flexibly designed according to the demands and show an outstanding device performance. However, OSCs with the capacity of solid-state crystallization (SSC) are developing too slowly to meet demands in productions and applications, due to their difficulties in molecular design and synthesis, unclear mechanism and high dependence on experimental conditions. In this work, in order to solve the problems, we synthesized an organic semiconductor capable of SSC at room temperature by adjusting the relationship between conjugated groups and functional groups. The thermodynamic and kinetic properties have been studied to discover the model of film SSC. Moreover, it can be purposefully controlled to prepare the high-quality crystals, and their corresponding organic electronic devices were further fabricated and discussed.     

Stabilization of the Closed-Ring Isomer of Spiropyran by Amide Naphthotube in Water and Its Application in Naked-Eye Detection of Toxic Paraoxon

The thermodynamically unstable, colourless closed-ring isomer of spiropyran can be stabilized in water by the anti-configurational isomer of amide naphthotube. The influence of the binding on the thermodynamics and kinetics of spiropyran have been studied. The complex was further used to prepare a test paper that allows naked-eye detection of toxic paraoxon.     

Rapid measurements of curcumin from complex samples coupled with magnetic biocompatibility molecularly imprinted polymer using electrochemical detection

Curcumin widely exists in food, and rapid selective and accurate detection of curcumin have great significance in chemical industry. In this experiment, a new magnetic biocompatibility molecularly imprinted polymer was prepared with nontoxic and biocompatible Zein to adsorb curcumin selectively. The polymer has high biocompatibility, good adsorption capacity, and specific adsorption for curcumin. Combined with portable electrochemical workstations, the polymer can be used to detect curcumin rapidly and cost‐effectively. Using curcumin as a template and Zein as the crosslinking agent, the polymers were synthesized on the surface of Fe₃O₄ particles for solid phase extraction. The experimental results showed that the polymer reached large adsorption capacity (32.12 mg/g) with fast kinetics (20 min). The adsorption characteristic of the polymer followed the Langmuir isotherm and pseudo‐second‐order kinetic models. Hexacyanoferrate was used as electrochemical probe to generate signals, and the linear range was 5–200 µg/mL for measuring curcumin. The experimental analysis showed that the polymer was an ideal material for selective accumulation of curcumin from complex samples. This approach has been successfully applied to the determination of curcumin in food samples with electrochemical detection, indicating that this is a feasible and practical technique.     

In‐situ preparation of porous monolithic polymer inside hollow fiber as a micro‐solid phase extraction device for glucocorticoids in cosmetics

Glucocorticoids have a certain whitening effect on the skin. However, frequent and long‐term use of cosmetics including glucocorticoids is harmful to health. Herein, we proposed a novel micro‐solid phase extraction method for the detection of prednisolone acetate, prednisone, and prednisolone in cosmetics coupled with high‐performance liquid chromatography. In this method, porous monolithic polymer micro‐extraction bars were prepared by “one‐step, one‐pot” in situ photopolymerization combined with sacrificial support in hollow fiber under water atmosphere. The crucial factors such as pH of sample solution, extraction, and elution times that influence micro‐extraction were optimized and found to be 9.0, 2 h, and 32 min, respectively. Under the optimum experimental conditions, the linear range of the calibration curves were from 5.0 to 2000 µg/L with correlation coefficients (R²) between 0.9922 and 0.9996. The limit of detection and limit of quantification were 1.5 µg/L and 5.0 µg/L, respectively, and the recoveries were found to be in range of 69.0–113.3%. The analysis of precision for intraday and interday were less than 10.40 and 10.59%. The device has been successfully achieved photopolymerization under water atmosphere. The results indicated that this method is simple, accurate, and satisfactory for the pretreatment and determination of glucocorticoids in complex cosmetics samples.     

Core‐Shell Structured Layered Lanthanide‐Organic Complexes with Stilbazolium‐type Dye Encapsulation for Multifunctional Performances

Host‐guest encapsulation of functional organic dye into a porous metal‐organic framework can give rise to the development of new functional materials. In this work, by intercalating the stilbazolium‐type dye (DEAST)I (4′‐diethylamino‐N‐methyl stilbazolium) into four lanthanide layered metal‐organic complexes (Ln‐LMOCs), i. e. {[Ln(BTB)(H₂O)₂]?3(DMF)?2(H₂O)}_n (Ln=La (1), Nd (2), Sm (3), Er (4)), four responsive (DEAST)I@Ln‐LMOC composites have been prepared, serving as multifunctional performance platform. The core–shell structures of (DEAST)I@Ln‐LMOC composites have been fully characterized by IR, UV/Vis, PXRD, SEM, TEM, TGA and ESR. Significantly, after intercalation of dyes, the (DEAST)I@Ln‐LMOC composites exhibit enhanced luminescent sensing properties in detecting Fe³⁺ with much higher water stabilities. The luminescent sensing behavior stems from the fluorescence resonance energy transfer (FRET) from the π‐electron‐rich BTB ligands to the Fe³⁺, and their higher water stabilities are induced by electrostatic interactions and lower porosity. Specially, the characteristic emissions of Sm³⁺ will not be affected after the encapsulation guest dyes, which provide a theoretical guide for the modulation of luminescence devices. Finally, better ion conductivities and diminished photocurrents can be achieved after the embedding of the functional organic dye. In all, the formation of (DEAST)I@Ln‐LMOC composites with core–shell structures can be utilized as a multifunctional platform with good stability.     

Understanding energetic disorder in electron-deficient-core-based non-fullerene solar cells

Recent advances in material design for organic solar cells(OSCs) are primarily focused on developing near-infrared nonfullerene acceptors, typically A-DA′D-A type acceptors(where A abbreviates an electron-withdrawing moiety and D, an electron-donor moiety), to achieve high external quantum efficiency while maintaining low voltage loss. However, the charge transport is still constrained by unfavorable molecular conformations, resulting in high energetic disorder and limiting the device performance. Here, a facile design strategy is reported by introducing the "wing"(alkyl chains) at the terminal of the DA′D central core of the A-DA′D-A type acceptor to achieve a favorable and ordered molecular orientation and therefore facilitate charge carrier transport. Benefitting from the reduced disorder, the electron mobilities could be significantly enhanced for the"wing"-containing molecules. By carefully changing the length of alkyl chains, the mobility of acceptor has been tuned to match with that of donor, leading to a minimized charge imbalance factor and a high fill factor(FF). We further provide useful design strategies for highly efficient OSCs with high FF.