Nonactivated Aziridine Synthesis by Intermolecular Polarity-Mismatched Carboamination of Unactivated Alkenes with Unactivated Alkyl Halides.

A general intermolecular polarity-mismatched carboamination reaction of unactivated alkenes with unactivated alkyl halides has been developed. A series of nonactivated alkyl-substituted aziridines were constructed in exclusive regioselectivity. The dual polarity-mismatched mechanism might be involved.

Improved Protein Removal Performance of PES Hollow-Fiber Ultrafiltration Membrane with Sponge-like Structure.

The research used polyethersulfone (PES) as a membrane material, polyvinylpyrrolidone (PVP) k30 and polyethylene glycol 400 (PEG 400) as water-soluble additives, and dimethylacetamide (DMAc) as a solvent to prepare hollow-fiber ultrafiltration membranes through a nonsolvent-induced phase separation (NIPS) process. The hydrophilic nature of PVP-k30 and PEG caused them to accumulate on the membrane surface during phase separation. The morphology, chemical composition, surface charge, and pore size of the PES membranes were evaluated by SEM, FTIR, zeta potential, and dextran filtration experiments. The paper also investigated how different spinning solution compositions affected membrane morphology and performance. The separation efficiency of membranes with four different morphologies was tested in single-protein and double-protein mixed solutions. The protein separation effectiveness of the membrane was studied through molecular weight cutoff, zeta potential, and static protein adsorption tests. In addition, the operating pressure and pH value were adjusted to improve ultrafiltration process conditions. The PES membrane with an intact sponge-like structure showed the highest separation factor of 11, making it a prime candidate membrane for the separation of bovine serum albumin (BSA) and lysozyme (LYS). The membrane had a minimal static protein adsorption capacity of 48 mg/cm2 and had excellent anti-fouling properties. When pH = 4, the BSA retention rate was 93% and the LYS retention rate was 23%. Furthermore, it exhibited excellent stability over a pH range of 1-13, confirming its suitability for protein separation applications.

Boosting CO2 chemical fixation over MOF-808 by the introduction of functional groups and defective Zr sites.

CO2 cycloaddition has emerged as a promising approach for producing value-added cyclocarbonates and mitigating greenhouse gas emissions. Although MOF-808 serves as a stable catalyst for cycloaddition, its limited activity constrains broader applications. Through the modification with a fluoride group via a ligand exchange method, F-MOF-808-1.5 exhibits exceptional performance, achieving a 98.8% conversion with 97.8% selectivity to epichlorohydrin carbonate-marking a substantial 100% improvement compared to pristine MOF-808. The defective Zr sites and the electron-withdrawing groups synergistically promote the ring opening of epoxides. Furthermore, the catalyst demonstrates high stability over multiple reaction cycles. Notably, without adding solvents and co-catalysts, F-MOF-808-1.5 outperforms most reported MOF-based catalysts.

Regioselective and Geometrically Controlled Heck 1,1-Diarylation of Unactivated Aliphatic Alkenes.

Pd-catalyzed double Heck reaction allows regioselective 1,1-diarylation of unactivated aliphatic alkenes. When two different aryl bromides are used, the second aryl rings are added trans to aliphatic chains in the main olefinic isomers, consistent with a mechanism of two consecutive Heck arylations at the terminal carbons.

Treatment of Aniline Wastewater by Membrane Distillation and Crystallization.

Aniline is a highly toxic organic pollutant with "carcinogenic, teratogenic and mutagenesis" characteristics. In the present paper, a membrane distillation and crystallization (MDCr) process was proposed to achieve zero liquid discharge (ZLD) of aniline wastewater. Hydrophobic polyvinylidene fluoride (PVDF) membranes were used in the membrane distillation (MD) process. The effects of the feed solution temperature and flow rate on the MD performance were investigated. The results showed that the flux of the MD process was up to 20 L·m-2·h-1 and the salt rejection was above 99% under the feeding condition of 60 °C and 500 mL/min. The effect of Fenton oxidation pretreatment on the removal rate of aniline in aniline wastewater was also investigated, and the possibility of realizing the ZLD of aniline wastewater in the MDCr process was verified.

Palladium-loaded ceramic membrane-catalyzed flow-through Suzuki-Miyaura reaction.

A general Pd-loaded ceramic membrane catalyzed Suzuki-Miyaura reaction in a flow-through membrane reactor is reported for the first time. Versatile (hetero)aryl bromides and chlorides proceeded well with an array of (hetero)aryl boronic acids. The consistently high activity of the catalytic membrane in eight cycles has proved its good stability and recyclability. Synthesis of drug molecules has further demonstrated that the catalytic membrane protocol is a powerful and comprehensive alternative to the traditional Suzuki-Miyaura cross-coupling.

Reductive-Delay Heck 1,1-Diarylation of Terminal Alkenes.

Pd-catalyzed chemo- and regiocontrollable 1,1-diarylation of unactivated aliphatic alkenes with two aryl halides was developed. Under the cationic reductive-delay Heck pathway, the first aryl insertion is followed by ß-H elimination, while the second aryl insertion is terminated by C-H bond formation.

Nickel-Catalyzed Chemo- and Regioselective Arylcyanation of ß,γ-Unsaturated Amides.

A nickel-catalyzed intermolecular arylcyanation of 8-aminoquinolinyl ß,γ-unsaturated amides is reported. The three-component reaction directly afforded diverse ß-cyano γ-aryl amides with exclusive chemo- and regioselectivity. The synthetic practicality of this approach is further demonstrated through multigram scale reaction, expanded transformations of the nitrile product, late-stage modification of complex molecules, and direct drug synthesis.

A simple and versatile synthesis strategy of hollow MOFs for CO2 separation and catalysis.

A novel single-solvent-interfacial strategy is proposed to synthesize hollow MOFs, fabricated at the two-phase interface originated from the self-deliquescence of hydration water in the metallic precursors and the solvents with low water solubility. The as-fabricated HMOFs with hierarchically porous structures exhibit significant enhancement in CO2 separation and catalysis.

Two-dimensional N-doped Pd/carbon for highly efficient heterogeneous catalysis.

A novel two-dimensional ZIF-derived Pd@CN material prepared via one-step calcination exhibits outstanding catalytic activity in heterogeneous hydrogenation. Its well-developed porous structure, low dimensions and low density make active sites more accessible. This facile and effective strategy can guide the synthesis of highly active and durable Pd@CN catalysts with specific morphologies.

Catalytic base-controlled regiodivergent heteronucleophilic hydrofunctionalization of ß,γ-unsaturated amides.

A general catalytic base-controlled regiodivergent nucleophilic hydrofunctionalization of both terminal and internal ß,γ-unsaturated amides has been reported. The atom-economical addition of various S/P-based nucleophiles was also exclusively chemoselective. More than 60 branched or linear hetero-substituted aliphatic amides were synthesized from common starting materials under transition-metal-free conditions. Preliminary mechanistic studies are consistent with our proposed divergent catalytic cycles.

Protective effects of collagen polypeptide from tilapia skin against injuries to the liver and kidneys of mice induced by d-galactose.

We wished to investigate the role of a tilapia skin collagen polypeptide (TSCP; molecular weight <3 kDa) in alleviating liver and kidney injuries in aging mice induced by d-galactose (d-gal) and its underlying mechanism of action. First, we characterized TSCP. TSCP was passed through a 3-kDa ultrafiltration membrane, desalted in water by a solid-phase extraction column, purified further by reverse phase-high performance liquid chromatography, and analyzed by electrospray ionization mass spectrometry and tandem mass spectrometry. TSCP contained 17 types of amino acids (AAs) and 41 peptide chains of length 7 AAs to 22 AAs. The content of free AAs and total AAs of TSCP was 13.5% and 93.79%, respectively. Next, we undertook animal experiments. Mice were injected once-daily with D-gal (300 mg/kg body weight, s.c.) for 8 weeks, and TSCP was administered simultaneously once-daily by intragastric gavage. TSCP could visibly improve the decreased body weight, depressed appetite, and mental deterioration of mice triggered by d-gal. TSCP could also alleviate d-gal-induced damage to the liver and kidneys according to histopathology (especially high-dose TSCP). Consistent with these macroscopic and pathologic changes, TSCP could also prevent d-gal-induced increases in serum levels of alanine aminotransferase, aspartate transaminase, alkaline phosphatase, lipid peroxidation, creatinine and uric acid, as well as decreases in serum levels of immunoglobulin (Ig)G and IgM. Moreover, TSCP improved the activities of superoxide dismutase, catalase, and glutathione peroxidase, but also inhibited the increases in the levels of malondialdehyde and inducible nitric oxide synthase expression in the liver and kidneys of d-gal-treated mice. These results suggest that TSCP can alleviate the injuries to the liver and kidneys in aging mice induced by d-gal, and that its mechanism of action might be, at least partially, associated with attenuation of oxidative stress and enhancement of immune function.

Extremely efficient and recyclable absorbents for oily pollutants enabled by ultrathin-layered functionalization.

Oils and organic solvents that leak into water bodies must be promptly removed to avoid ecological disasters, for example, by selective absorption using oleophilic absorbents. However, it remains a challenge for the low-cost synthesis of efficient and recyclable absorbents for oily pollutants. By surface functionalization to inexpensive polyurethane (PU) foams, we synthesize oil absorbents exhibiting the highest absorption capacity and the best recyclability among all polymeric absorbents. The synthesis is enabled by atomic layer deposition of ∼5 nm-thick Al2O3 transition layer onto the skeleton surface of PU foams, followed by coupling a single-molecule layer of silanes to the Al2O3 layer. The sub-10 nm functionalization layer provides the PU foam an outstanding water-repelling and oil-absorbing functionality without compromising its high porosity and elasticity. The functionalized foam is able to quickly absorb oily pollutants spread on water surfaces or precipitated in water with a capacity more than 100 times its own weight. This ultrathin-layer-functionalization method is also applicable to renewable porous biomaterials, providing a sustainable solution for oil spills. Moreover, we propose devices than can continuously operate to efficiently collect oil spills from water surfaces based on the functionalized PU foam developed in this work.

A two-dimensional zeolitic imidazolate framework with a cushion-shaped cavity for CO2 adsorption.

A new two-dimensional zeolitic imidazolate framework (named as ZIF-L) was synthesized in zinc salt and 2-methylimidazole (Hmim) aqueous solution at room temperature. ZIF-L (Zn(mim)2·(Hmim)1/2·(H2O)3/2 or C10H16N5O3/2Zn) has unique cushion-shaped cavities and leaf-like crystal morphology, and exhibits excellent CO2 adsorption properties.