Search Results (13)

Mycotoxins commonly contaminate grains and traditional Chinese medicinal materials, posing serious health risks to humans and animals. To address this issue, a magnetic microporous organic network (MMON) was synthesized via an in situ growth method and Sonogashira–Hagihara coupling for the simultaneous adsorption of seven mycotoxins, followed by UPLC-MS/MS detection. The optimized MMON featured a high surface area, uniform micropores, and rapid magnetic separation within 5 s. Structural and compositional analyses confirmed its tailored architecture, while DFT calculations revealed a pore confinement effect, π–π stacking, and hydrophobic interactions as the primary adsorption mechanisms. A magnetic solid-phase extraction (MSPE) method using 8 mg of MMON achieved adsorption equilibrium within 10 s in 5 mL of a 4 mg/L mycotoxin standard solution. The material maintained over 95% efficiency across ten reuse cycles at a low cost. Under optimal conditions, an MSPE-UPLC-MS/MS method with a low detection limit (0.002–0.15 μg/L), wide linear range (0.01–100.0 μg/L), large enrichment factor (20.1–21.9), low adsorbent dosage, and short extraction time was developed. The determination of mycotoxins in complex grain-based foods and herbal products was also realized with recoveries of 81.32% to 116.10%. This work offers a rapid, cost-effective, and high-throughput approach for mycotoxin detection, supporting quality control in food and herbal product safety. Full article

The visible-light-driven photocatalytic production of hydrogen peroxide (H₂O₂) is currently an emerging approach for transforming solar energy into chemical energy. In general, the photocatalytic process for producing H₂O₂ includes two pathways: the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). However, the utilization efficiency of ORR surpasses that of WOR, leading to a discrepancy with the low oxygen levels in natural water and thereby impeding their practical application. Herein, we report a novel donor–bridge–acceptor (D-B-A) organic polymer conjugated by the Sonogashira–Hagihara coupling reaction with tetraphenylethene (TPE) units as the electron donors, acetylene (A) as the connectors and pyrene (P) moieties as the electron acceptors. Notably, the resulting TPE-A-P exhibits a remarkable solar-to-chemical conversion of 1.65% and a high BET-specific surface area (1132 m²·g⁻¹). Furthermore, even under anaerobic conditions, it demonstrates an impressive H₂O₂ photosynthetic efficiency of 1770 μmol g⁻¹ h⁻¹, exceeding the vast majority of previously reported photosynthetic systems of H₂O₂. The outstanding performance is attributed to the effective separation of electrons and holes, along with the presence of sufficient reaction sites facilitated by the incorporation of alkynyl electronic bridges. This protocol presents a successful method for generating H₂O₂ via a water oxidation reaction, signifying a significant advancement towards practical applications in the natural environment. Full article

Stable palladium (II) complexes, incorporating a double (N-benzoylthiourea) arrangement bonded to a complex heterocyclic scaffold, are used as precursors of catalytic species able to promote Suzuki–Miyaura, Mizoroki–Heck, Hiyama, Buchwald–Hartwig, Hirao and Sonogashira–Hagihara cross-coupling transformations in water. These sustainable processes are chemoselective and very versatile. The nanoparticles responsible for these catalytic reactions were analyzed and studied. Their usefulness is demonstrated after several tests and analyses. The heterogeneous character of this species in water was also confirmed. Full article

Conjugated microporous polymers (CMP) as porous functional materials have received considerable attention due to their unique structures and fascinating properties for the adsorption and degradation of dyes. Herein, a triazine-conjugated microporous polymer material with rich N-donors at the skeleton itself was successfully synthesized via the Sonogashira–Hagihara coupling by a one–pot reaction. These two polymers had Brunauer–Emmett–Teller (BET) surface areas of 322 and 435 m²g⁻¹ for triazine-conjugated microporous polymers (T-CMP) and T-CMP-Me, respectively. Due to the porous effects and the rich N-donor at the framework, it displayed a higher removal efficiency and adsorption performance compared to cationic-type dyes and selectivity properties for (methylene blue) MB⁺ from a mixture solution of cationic-type dyes. Furthermore, the T-CMP-Me could quickly and drastically separate MB⁺ and (methyl orange) MO⁻ from the mixed solution within a short time. Their intriguing absorption behaviors are supported by ¹³C NMR, UV−vis absorption spectroscopy, scanning electron microscopy, and X-ray powder diffraction studies. This work will not only improve the development of porous material varieties, but also demonstrate the adsorption or selectivity of porous materials for dyes from wastewater. Full article

We have successfully synthesized two types of two-dimensional conjugated microporous polymers (CMPs), Py-BSU and TBN-BSU CMPs, by using the Sonogashira cross-coupling reaction of BSU-Br₂ (2,8-Dibromothianthrene-5,5′,10,10′-Tetraoxide) with Py-T (1,3,6,8-Tetraethynylpyrene) and TBN-T (2,7,10,15-Tetraethynyldibenzo[g,p]chrysene), respectively. We characterized the chemical structure, morphology, physical properties, and potential applications of these materials using various analytical instruments. Both Py-BSU and TBN-BSU CMPs showed high thermal stability with thermal decomposition temperatures (T_d10) up to 371 °C and char yields close to 48 wt%, as determined by thermogravimetric analysis (TGA). TBN-BSU CMPs exhibited a higher specific surface area and porosity of 391 m² g⁻¹ and 0.30 cm³ g⁻¹, respectively, due to their large micropore and mesopore structure. These CMPs with extended π-conjugated frameworks and high surface areas are promising organic electroactive materials that can be used as electrode materials for supercapacitors (SCs) and gas adsorption. Our experimental results demonstrated that the TBN-BSU CMP electrode had better electrochemical characteristics with a longer discharge time course and a specific capacitance of 70 F g⁻¹. Additionally, the electrode exhibited an excellent capacitance retention rate of 99.9% in the 2000-cycle stability test. The CO₂ uptake capacity of TBN-BSU CMP and Py-BSU CMP were 1.60 and 1.45 mmol g⁻¹, respectively, at 298 K and 1 bar. These results indicate that the BSU-based CMPs synthesized in this study have potential applications in electrical testing and CO₂ capture. Full article

Due to the frequent oil/organic solvent leakage, efficient oil/water separation has attracted extensive concern. However, conventional porous materials possess nonpolar building units, which reveal relatively weak affinity for polar organic molecules. Here, two different polarities of superhydrophobic porous aromatic frameworks (PAFs) were synthesized with respective orthoposition and paraposition C=O groups in the PAF linkers. The conjugated structure formed by a large number of alkynyl and benzene ring structures enabled porous and superhydrophobic quality of PAFs. After the successful preparation of the PAF solids, PAF powders were coated on polyester fabrics by a simple dip-coating method, which endowed the resulting polyester fabrics with superhydrophobicity, porosity, and excellent stability. Based on the unique structure, the oil/water separation efficiency of two superhydrophobic flexible fabrics was more than 90% for various organic solvents. Polar LNU-26 PAF showed better separation performance for the polar oils. This work takes the lead in adopting the polar groups as building units for the preparation of porous networks, which has great guiding significance for the construction of advanced oil/water separation materials. Full article

Eucalyptus plants have attracted the attention of researchers and environmentalists worldwide because they are a rapidly growing source of wood and a source of oil used for multiple purposes. The main and the most important oil component is 1,8-cineole (eucalyptol: 60–85%). This review summarizes the literature reported to date involving the use of 1,8-cineole for the treatment of disorders. Additionally, we describe our efforts in the use of eucalyptol as a solvent for the synthesis of O,S,N-heterocycles. Solvents used in chemistry are a fundamental element of the environmental performance of processes in corporate and academic laboratories. Their influence on costs, safety and health cannot be neglected. Green solvents such as bio-based systems hold considerable additional promise to reduce the environmental impact of organic chemistry. The first section outlines the process leading to our discovery of an unprecedented solvent and its validation in the first coupling reactions. This section continues with the description of its properties and characteristics and its reuse as reported in the various studies conducted. The second section highlights the use of eucalyptol in a series of coupling reactions (i.e., Suzuki–Miyaura, Sonogashira–Hagihara, Buchwald–Hartwig, Migita–Kosugi–Stille, Hiyama and cyanation) that form O,S,N-heterocycles. We describe the optimization process applied to reach the ideal conditions. We also show that eucalyptol can be a good alternative to build heterocycles that contain oxygen, sulfur and nitrogen. These studies allowed us to demonstrate the viability and potential that bio solvents can have in synthesis laboratories. Full article

Nitrogen-rich porous networks with additional polarity and basicity may serve as effective adsorbents for the Lewis electron pairing of iodine molecules. Herein a carbazole-functionalized porous aromatic framework (PAF) was synthesized through a Sonogashira–Hagihara cross-coupling polymerization of 1,3,5-triethynylbenzene and 2,7-dibromocarbazole building monomers. The resulting solid with a high nitrogen content incorporated the Lewis electron pairing effect into a π-conjugated nano-cavity, leading to an ultrahigh binding capability for iodine molecules. The iodine uptake per specific surface area was ~8 mg m⁻² which achieved the highest level among all reported I₂ adsorbents, surpassing that of the pure biphenyl-based PAF sample by ca. 30 times. Our study illustrated a new possibility for introducing electron-rich building units into the design and synthesis of porous adsorbents for effective capture and removal of volatile iodine from nuclear waste and leakage. Full article

A new fluorogenic bis-calix[4]arene-carbazole compound (3) with an enlarged intramolecular cavity able to be involved in host–guest chemistry with large organic guests was designed. Its synthesis was accomplished for the first time using a Sonogashira–Hagihara cross-coupling reaction in the final step. The calixarene receptor was structurally characterized by FTIR and ¹H/¹³C/2D NMR techniques and its photophysical properties evaluated. The ability of 3 to form supramolecular complexes with fullerenes (C₆₀ and C₇₀) was evaluated through fluorometric titration experiments. The value of the binding constants (K_3:C60 = 1.39 × 10⁵ M⁻¹ and K_3:C70= 6.88 × 10⁴ M⁻¹), and the free energy changes for the inclusion complexation (G_3:C60 = −29.33 kJ/mol and G₃:_C70 = −27.60 kJ/mol), revealed a high sensitivity of the calixarene-carbazole host for both fullerenes. The host molecule was shown to be particularly selective towards fullerene C₆₀. Full article

The awareness of sustainability led to increasing global demand for processes that use lower energy, produce reduced waste, use fewer organic solvents, and offer improved selectivity. In this context, mechanochemistry re-emerged as a powerful green methodology. The conventional synthesis and functionalization of calixarenes, both on the upper and lower rim, has been the subject of numerous studies but only a few were reported using a mechanochemical approach. Herein, we present new mechanically assisted key synthetic steps towards a more sustainable route to calix[4]arenes functionalized in the lower rim. Full article

Hexacarboxylates are promising linkers for MOFs such as NU-109 or NU-110, which possess large values for surfaces and pore volumina. Starting from 2,4,6-tris(bromoaryl)-1,3,5-triazines, palladium-catalyzed cross coupling reactions (Suzuki-Miyaura, Sonogashira-Hagihara) form elongated hexacarboxylate linkers. Eight new 2,4,6-tris(biphenyl) and 2,4,6-tris(phenylethynylphenyl) 1,3,5-triazines have been prepared in quantities ranging from 40 mg to 1.1 g. In five cases, one of the arms of the linker carries an additional functionality (NO₂ or OMe). Full article

Microporous organic polymers and related porous materials have been applied in a wide range of practical applications such as adsorption, catalysis, adsorption, and sensing fields. However, some limitations, like wide pore size distribution, may limit their further applications, especially for adsorption. Here, micro- and ultra-microporous frameworks (HBPBA-D and TBBPA-D) were designed and synthesized via Sonogashira–Hagihara coupling of six/eight-arm bromophenyl adamantane-based “knots” and alkynes-type “rod” monomers. The BET surface area and pore size distribution of these frameworks were in the region of 395–488 m² g⁻¹, 0.9–1.1 and 0.42 nm, respectively. The as-made prepared frameworks also showed good chemical ability and high thermal stability up to 350 °C, and at 800 °C only 30% mass loss was observed. Their adsorption capacities for small gas molecules such as CO₂ and CH₄ was 8.9–9.0 wt % and 1.43–1.63 wt % at 273 K/1 bar, and for the toxic organic vapors n-hexane and benzene, 104–172 mg g⁻¹ and 144–272 mg g⁻¹ at 298 K/0.8 bar, respectively. These are comparable to many porous polymers with higher BET specific surface areas or after functionalization. These properties make the resulting frameworks efficient absorbent alternatives for small gas or toxic vapor capture, especially in harsh environments. Full article

A novel π-stacked polymer based on a pseudo–meta–linked [2.2]paracyclophane moieties was synthesized by Sonogashira-Hagihara coupling. The UV-vis absorption spectra of the synthesized polymer and model compounds revealed an extension of the conjugation length owing to the through-space conjugation. The optical properties of the π-stacked dimer with the pseudo–meta–linked [2.2]paracyclophane unit were compared with those of the corresponding dimers with the pseudo–ortho– and pseudo–para–linked [2.2]paracyclophane units. Full article