Fabrication of sulfobutylether-ß-cyclodextrin/glabridin inclusion complex for promoting bioactivities.

As the main active compound of Glycyrrhiza glabra L., glabridin (GLD) has been shown to have multiple bioactivities, whereas the clinical application of GLD is restricted by its low water solubility. In this study, GLD was encapsulated into a sulfobutylether-ß-cyclodextrin (SBE-ß-CD)-based inclusion complex (SBE-ß-CD/GLD) by the freeze-drying method. The materials characterization, antibacterial activity, stimulated cellular behavior and in vivo full-thickness diabetic wound healing ability of the hydrogels were assessed and analyzed. The successful encapsulation of the inclusion complex was confirmed by ultraviolet (UV) visible spectroscopy, Fourier transform infrared (FT-IR), X-ray diffractometer (XRD), scanning electron microscope (SEM), and nuclear magnetic resonance (NMR). SBE-ß-CD as an excipient significantly enhances the water solubility of GLD, and SBE-ß-CD/GLD showed excellent biocompatibility on human vascular endothelial cells (HUVECs) and erythrocytes. The SBE-ß-CD/GLD inclusion complex exerted a pronounced antibacterial activity on Staphylococcus aureus and Escherichia coli in vitro. The SBE-ß-CD/GLD inclusion complex markedly enhanced the antioxidant activity compared with free GLD. The SBE-ß-CD/GLD inclusion complex potently accelerates the healing of full-thickness skin defects by inhibiting inflammation. The outcomes suggest that SBE-ß-CD could be used as a promising drug delivery system for the clinical application of GLD.

Oxidant-Assisted Sulfonylation/Cyclization Cascade Synthesis of Alkylsulfonylated Oxindoles via the Insertion of SO2.

An oxidant-assisted tandem sulfonylation/cyclization of electron-deficient alkenes with 4-alkyl-substituted Hantzsch esters and Na2S2O5 for the preparation of 3-alkylsulfonylated oxindoles under mild conditions in the absence of a photocatalyst and transition metal catalyst is established. The mechanism studies show that the alkyl radicals, which come from the cleavage of the C-C bond in 4-substituted Hantzsch esters under oxidant conditions, subsequently undergo the in situ insertion of sulfur dioxide to generate the crucial alkylsulfonyl radical intermediates. This three-component reaction provides an efficient and facile route for the construction of alkylsulfonylated oxindoles and avoids the use of highly toxic alkylsulfonyl chlorides or alkylsulfonyl hydrazines as alkylsulfonyl sources.

Regioselective synthesis of N-containing polycyclic compounds via radical annulation cyclization of 1,7-dienes with aldehydes.

A convenient method for oxidant-promoted radical cascade acylation or decarbonylative alkylation of 1,7-dienes with aldehydes has been established. This method allows for the rapid construction of N-containing polycyclic skeletons in a highly regio- and stereoselective manner. This transformation provides a simple and efficient method for the preparation of a range of tetrahydro-6H-indeno[2,1-c]quinolinone derivatives by sequential formation of three new carbon-carbon bonds. Additionally, this radical cascade cyclization can selectively convert aldehydes into aroyl/primary aliphatic acyl radicals and secondary or tertiary alkyl radicals.

Effect of branched 1,4-butanediol citrate oligomers with different molecular weights on toughness and aging resistance of glycerol plasticized starch.

The thermoplastic starch with glycerol is easy to retrograde and sensitive to hygroscopicity. In this study, branched 1,4-butanediol citrate oligomers with different molecular weights (P1, P2, and P3) are synthesized, and then mixed with glycerol (G) as the co-plasticizers to prepare thermoplastic starch (CS/PG). The results show that the molecular weight and branching degree of the branched 1,4-butanediol citrate oligomers increase as reaction time prolongs. Compared with glycerol plasticized starch, the thermoplastic starch films with branched 1,4-butanediol citrate oligomers/glycerol (10 wt%/20 wt%) have a better toughness, transmittance, and aging resistance, and have a lower crystallinity, hygroscopicity, and thermal stability. The toughness, transmittance, and aging resistance of CS/PG films are positively correlated with the molecular weight of the branched 1,4-butanediol citrate oligomers. These are due to the fact that the branched 1,4-butanediol citrate oligomer with a high molecular weight could form a stronger hydrogen bond and the more stable cross-linked structure with starch chains than that with a lower molecular weight. The elongation at break of CS/P3G film stored for 3 and 30 d are 98.0 % and 88.1 %, respectively. The mixture of branched butanediol citrate oligomers and glycerol, especially P3/G, has a potential application in the preparation of thermoplastic starch.

Electrochemical Oxidative (4 + 2) Cyclization of Anilines and o-Phenylenediamines for the Synthesis of Phenazines.

Phenazines, crucial constituents of nitrogen-containing heterocycles, widely exist in functional compounds. Herein, we report an anodic oxidative (4 + 2) cyclization between anilines and o-phenylenediamines for the uniform construction of phenazines in a simple undivided cell. Dual C-H amination followed by oxidation represents an outstanding step and atom efficiency. A sequence of phenazines is produced with excellent functional group tolerance at room temperature.

Electro-oxidative three-component cascade coupling of isocyanides with elemental sulfur and amines for the synthesis of 2-aminobenzothiazoles.

2-Aminobenzothiazoles are commonly encountered in various functional compounds. Herein, we disclose an electro-oxidative three-component reaction for the effective synthesis of 2-aminobenzothiazoles under mild conditions, utilizing non-toxic and abundant elemental sulfur as the sulfur source. Both aliphatic amines and aryl amines demonstrate good compatibility at room temperature, highlighting the broad functional group tolerance of this approach. Additionally, elemental selenium demonstrated reactivities comparable to those of elemental sulfur.

Formulation analysis of functional fragrance via polar-gradient extraction method and chemometrics pattern recognition.

In this study, characteristic components of 15 natural flavors was analyzed by the polar-gradient extraction (PGE) technique in combination with GC-MS and chemometrics pattern recognition. The obtained results were utilized for the traceability of 4 functional fragrance formulations. The optimal PGE system consisting of 5 different polar solvents, was developed based on similarity-intermiscibility theory. Four chemometrics pattern recognition models including PCA, HCA, PLS-DA, and OPLS-DA were constructed based on the characteristic component database constituting 15 natural flavors. These models were used to trace 4 functional fragrance formulations. The experimental results obtained were found to be satisfactory and accurate. The combination of PGE technique and chemometric pattern recognition methods provides theoretical guidance for the analysis of characteristic components of natural flavors and the traceability of functional fragrance formulations. This approach can be promoted in various fields such as food, traditional Chinese medicine, and cosmetics.

Recent Advances in the Application of P(III)-Nucleophiles to Create New P-C Bonds through Michaelis-Arbuzov-Type Rearrangement.

Organophosphorus compounds have long been considered valuable in both organic synthesis and life science. P(III)-nucleophiles, such as phosphites, phosphonites, and diaryl/alkyl phosphines, are particularly noteworthy as phosphorylation reagents for their ability to form new P-C bonds, producing more stable, ecofriendly, and cost-effective organophosphorus compounds. These nucleophiles follow similar phosphorylation routes as in the functionalization of P-H bonds and P-OH bonds. Activation can occur through photocatalytic, electrocatalytic, or thermo-driven reactions, often in coordination with a Michaelis-Arbuzov-trpe rearrangement process, to produce the desired products. As such, this review offers a thorough overview of the phosphorylated transformation and potential mechanisms of P(III)-nucleophiles, specifically focusing on developments since 2010. Notably, this review may provide researchers with valuable insights into designing and synthesizing functionalized organophosphorus compounds from P(III)-nucleophiles, guiding future advancements in both research and practical applications.

Photoredox-Catalyzed Alkylarylation of N-Aryl Bicyclobutyl Amides with α-Carbonyl Alkyl Bromides: Access to 3-Spirocyclobutyl Oxindoles.

A visible-light-induced radical alkylarylation of N-aryl bicyclobutyl amides with α-carbonyl alkyl bromides for the synthesis of functionalized 3-spirocyclobutyl oxindoles is described in which ß-selective radical addition of the alkyl radical to N-aryl bicyclobutyl amides forms a key radical intermediate followed by interception with intrinsic arene functional group. This approach can be applicable to a wide range of α-carbonyl alkyl bromides, including primary, secondary, and tertiary α-bromoalkyl esters, ketones, nitriles, and nitro compounds.

Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles.

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis-Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and 31P NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation.

Visible-light-induced synthesis of 2,4-disubstituted quinolines from o-vinylaryl isocyanides and oxime esters.

A visible-light-induced radical cyclization reaction of o-vinylaryl isocyanides and oxime esters to access various 2,4-disubstituted quinolines was disclosed. Oxime esters were employed as acyl radical precursors via the carbon-carbon bond cleavage. It provided an effective way for the synthesis of 2-acyl-4-arlysubstituted quinolines under mild conditions and exhibited good functional group tolerance and substrate applicability.

A state-of-the-art review on biomass-derived carbon materials for supercapacitor applications: From precursor selection to design optimization.

Biomass-derived carbon materials have the characteristics of a wide range of precursor sources, controllable carbon nano-dimension, large specific surface area and abundant heteroatoms doping. At present, biomass-derived carbon materials have been widely used in electrochemical energy storage devices, especially the research and development of biomass-derived carbon materials for supercapacitors has become mature and in-depth. Therefore, it is of importance to summarize the advanced technologies and strategies for optimizing biomass-derived carbon materials for supercapacitors, which will effectively promote the further development of high-performance supercapacitors. In this review, the recent research progress of biomass-derived carbon materials is provided in detail, including the selection of biomass precursors, the design of carbon nano-dimension and the theory of heteroatom doping. Besides, the preparation methods of biomass-derived carbon materials and the related processes of optimizing the electrochemical performance are also summarized. This review ends with the perspectives for future research directions and challenges in the field of biomass-derived carbon materials for electrochemical applications. This review aims to provide helpful reference information for the nano-dimensional design and electrochemical performance optimization of biomass-derived carbon materials for the practical application of supercapacitors.

Encapsulation of lipase in zeolitic imidazolate framework-8 induced by polyethyleneimine to form a honeycomb structure with enhanced activity.

Embedding an enzyme in the metal-organic frameworks (MOFs) gives good protection to the fragile enzyme. However, this may also restrain the enzyme activity because of the decreased substrate accessibility. Encapsulation of lipase AK from Pseudomonas fluorescens for preparing the enzyme-MOF composite (AK@ZIF-8-PEI) was performed through a new strategy based on polyethyleneimine and enzyme induced in-situ growth of zeolitic imidazolate framework-8 (ZIF-8). Characterizations indicate that AK@ZIF-8-PEI has a honeycomb structure and the hierarchical porosity formed during the preparation, which provides adequate mass transfer channels for catalytic applications. Activity evaluation shows that specific activity of AK@ZIF-8-PEI is 8-fold than the commercial lipase powder. AK@ZIF-8-PEI is demonstrated as an efficient catalyst in kinetic resolution of α-naphthol enantiomers through enantioselective transesterification. Within 12 h, the conversion and substrate enantiomeric excess (ees) reaches 49.8 % and 96.4 %, achieving an improved resolution than previous researches.

Photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access 2,4-disubstituted quinolines.

We herein report an efficient photoredox radical cyclization reaction of o-vinylaryl isocyanides with acyl chlorides to access a wide range of 2,4-disubstituted quinolines. Preliminary mechanism experiment results suggested that this reaction was initiated by an acyl radical generated from acyl chlorides through a single-electron-transfer (SET) process. This transformation showed good substrate suitability and functional group compatibility at room temperature.

Recent advances in ring-opening of cyclobutanone oximes for capturing SO2, CO or O2via a radical process.

Cyclobutanone oximes and their derivatives are pivotal core structural motifs in organic chemistry. Iminyl-radical-triggered C-C bond cleavage of cyclobutanone oximes delivers an efficient strategy to produce stable distal cyano-substituted alkyl radicals, which can capture SO2, CO or O2 to form cyanoalkylsulfonyl radicals, cyanoalkylcarbonyl radicals or cyanoalkoxyl radicals under mild conditions. In the past several years, cyanoalkylsulfonylation/cyanoalkylcarbonyaltion/cyanoalkoxylation has attracted a lot of interest. In this updated report, the strategies for trapping SO2, CO or O2via iminyl-radical-triggered ring-opening of cyclobutanone oximes are summarized.

Ruthenium-Catalyzed 1,6-Hydroalkylation of para-Quinone Methides with Ketones via the in Situ Activation of C(sp3)-H Bonds.

A simple and efficient method for the ruthenium-catalyzed 1,6-hydroalkylation of para-quinone methides (p-QMs) with ketones via the in situ activation of C(sp3)-H bonds has been disclosed. Without the need for preactivation of the substrates and oxidant, a broad range of p-QMs and ketones are well tolerated, producing the expected 1,6-hydroalkylation products with moderate to good yields. Step-by-step control experiments and DFT calculation were conducted systematically to gain insights for the plausible reaction mechanism. This finding may have potential application in the selective diarylmethylation of ketones at the α-C position in organic synthesis.

Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles.

A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement for the synthesis of ß-ketophosphine oxides, ß-ketophosphinates, and ß-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles are tolerated in the transformation, generating the desired ß-keto-organophosphorus compounds as a valuable class of phosphorus-containing intermediates with good to excellent yields. In addition, the possible mechanism and kinetic studies for the reaction have been explored by step-by-step control experiments and competitive experiments, and the results proved that this transformation may follow second-order chemical kinetics as well as involve a radical process.

Visible-Light-Induced Synthesis of Alkylsulfonated Isoquinolinones from 2-Aryl Indoles/Benzimidazoles through Insertion of Sulfur Dioxide.

A visible-light-induced three-component reaction of 2-aryl indoles/benzimidazoles, Hantzsch esters, and sodium pyrosulfite through a radical cascade cyclization process with the insertion of sulfur dioxide is described. It provides a novel and powerful way for the synthesis of alkylsulfonated isoquinolinones. Hantzsch esters and Na2S2O5 are employed as alkyl radical precursors and SO2 surrogate, respectively. This transformation exhibits good functional group tolerance and substrate applicability under mild conditions.

Visible-Light-Promoted Decarboxylative Alkylation/Cyclization of Vinylcycloalkanes.

An efficient strategy for visible-light-promoted decarboxylative alkylation of vinylcyclopropanes with alkyl N-(acyloxy)phthalimide esters through the dual C-C bond and single N-O bond cleavage, employing triphenylphosphine and lithium iodide as the photoredox system to synthesize 2-alkylated 3,4-dihydronaphthalenes, has been established. This alkylation/cyclization involves a radical process and undergoes a sequence of N-(acyloxy)phthalimide ester single-electron reduction, N-O bond cleavage, decarboxylative, alkyl radical addition, C-C bond cleavage, and intramolecular cyclization. Moreover, using the photocatalyst Na2-Eosin Y instead of triphenylphosphine and lithium iodide, the vinyl transfer products are acquired when vinylcyclobutanes or vinylcyclopentanes are utilized as alkyl radical receptors.

A novel S,N-rich MOF for efficient recovery of Au(III): Performance and mechanism.

A novel S,N-rich MOF with adenine and 4,4'-thiodiphenol as organic ligands was synthesized via the one-step solvothermal method, and used for gold recovery. The pH impact, adsorption kinetics, isotherms, thermodynamics, selectivity, and reusability were investigated accordingly. The adsorption and desorption mechanism were also explored comprehensively. The electronic attraction, coordination, and in situ redox account for the Au(III) adsorption. The Au(III) adsorption is affected strongly by the pH of solutions, and best at pH of 2.57. The MOF exhibits exceptional adsorption capacity as high as 3680 mg/g at 55 °C, fast kinetics with 8 min for 9.6 mg/L Au(III), and excellent selectivity for gold ion in real e-waste leachates. The adsorption process of gold on the adsorbent is endothermic and spontaneous, and influenced visibly by temperature. The adsorption ratio still maintained 99% after seven adsorption-desorption cycles. The column adsorption experiments show that the MOF has outstanding selectivity for Au(III) with 100% of removal efficiency in a complex solution containing Au, Ni, Cu, Cd, Co, and Zn ions. A glorious adsorption with a breakthrough time of 532 mins was obtained for the breakthrough curve. This study not only provides an efficient adsorbent for gold recovery, but also guidance for designing new materials.