Synthesis of cryptands with di-yne units via acetylenic homocoupling reactions of C3 tripodands

Cryptands with di-yne units were obtained in good yields by the acetylenic homocoupling reaction of tripodands possesing terminal ethynyl units on the pendant arms. The coupling reactions also led to isomeric bismacrocylic compounds, and the shifting of the process toward the products of intramolecular or intermolecular coupling reactions was influenced by the structure of tripodands and by the coupling reaction conditions.     

Sustainable Catalysis: Rational Pd Loading on MIL‐101Cr‐NH2 for More Efficient and Recyclable Suzuki–Miyaura Reactions

Palladium nanoparticles have been immobilized into an amino‐functionalized metal–organic framework (MOF), MIL‐101Cr‐NH₂, to form Pd@MIL‐101Cr‐NH₂. Four materials with different loadings of palladium have been prepared (denoted as 4‐, 8‐, 12‐, and 16 wt %Pd@MIL‐101Cr‐NH₂). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier‐transform infrared (FTIR) spectroscopy, powder X‐ray diffraction (PXRD), N₂‐sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL‐101Cr‐NH₂, electron tomography was employed to reconstruct the 3D volume of 8 wt %Pd@MIL‐101Cr‐NH₂ particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high‐energy X‐rays (60 keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki–Miyaura cross‐coupling reaction. The best catalytic performance was obtained with the MOF that contained 8 wt % palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6 nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15 mol %). The material can be recycled at least 10 times without alteration of its catalytic properties.     

Thermal and optical properties of some phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s

A series of phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s was prepared by polycondensation reaction of an aromatic dianhydride, namely 1,4‐[2‐(6‐oxido‐6H‐dibenz<c,e><1,2>oxaphosphorin‐6‐yl)]‐naphthalene‐bis(trimellitate)dianhydride, with different aromatic diamines containing 1,3,4‐oxadiazole ring. A solution imidization procedure was used to convert quantitatively the poly(amic acid) intermediates to the corresponding polyimides. The chemical structures of the monomers and polymers were confirmed by Fourier transform infrared, ¹H NMR and ³¹P NMR spectroscopy. The polymers were easily soluble in polar solvents such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide and tetrahydrofuran. They exhibited good thermal properties having the decomposition temperature above 380°C and the glass transition temperature in the range of 201–232°C. Due to the presence of phosphorus the polymers gave high char yield in termogravimetric analysis, hence good flame retardant properties. Optical properties were analyzed in solution by using UV–vis and photoluminescence spectroscopy. Solutions of the polymers in NMP exhibited photoluminescence in the blue region. Copyright © 2010 John Wiley & Sons, Ltd.     

Green Synthesis,Characterization, and Antibacterial Properties of Silver Nanoparticles Obtained by Using Diverse Varieties of Cannabis sativa Leaf Extracts

Cannabis sativa L. (hemp) is a plant used in the textile industry and green building material industry, as well as for the phytoremediation of soil, medical treatments, and supplementary food products. The synergistic effect of terpenes, flavonoids, and cannabinoids in hemp extracts may mediate the biogenic synthesis of metal nanoparticles. In this study, the chemical composition of aqueous leaf extracts of three varieties of Romanian hemp (two monoecious, and one dioecious) have been determined by Fourier-Transformed Infrared spectroscopy (FT-IR), high-performance liquid chromatography, and mass spectrometry (UHPLC-DAD-MS). Then, their capability to mediate the green synthesis of silver nanoparticles (AgNPs) and their pottential antibacterial applications were evaluated. The average antioxidant capacity of the extracts had 18.4 ± 3.9% inhibition determined by 2,2-diphenyl-1-picrylhydrazyl (DPPH^•) and 78.2 ± 4.1% determined by 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS™) assays. The total polyphenolic content of the extracts was 1642 ± 32 mg gallic acid equivalent (GAE) L⁻¹. After this, these extracts were reacted with an aqueous solution of AgNO₃ resulting in AgNPs, which were characterized by UV−VIS spectroscopy, FT-IR, scanning electron microscopy (SEM-EDX), and dynamic light scattering (DLS). The results demonstrated obtaining spherical, stable AgNPs with a diameter of less than 69 nm and an absorbance peak at 435 nm. The mixture of extracts and AgNPs showed a superior antioxidant capacity of 2.3 ± 0.4% inhibition determined by the DPPH^• assay, 88.5 ± 0.9% inhibition as determined by the ABTS^•+ assay, and a good antibacterial activity against several human pathogens: Escherichia coli, Klebsiella pneumoniae, Pseudomonas fluorescens, and Staphylococcus aureus.     

Silver Nanoparticles Incorporated on Natural Clay as an Inhibitor against the New ISO SS Bacteria Isolated from Sewage Sludge,Involved in Malachite Green Dye Oxidation

A facile, ecofriendly, and cost-effective method was developed to prepare a microporous material based on natural chemically modified bentonite with silver ions (BN-Ag⁰). This material presents a good catalytic activity against Malachite Green (MG) dye and bacteriostatic activity against a newly isolated bacterium from sewage sludge named hereafter “ISO SS” and Escherichia coli (E. coli). BN-Ag⁰ was characterized by the following methods: energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), Fourier-transform infrared (FTIR) spectroscopy, temperature programmed desorption (TPD) and X-ray Diffraction (XRD). The new bacterium ISO SS, was isolated using the technique of isolating a pure culture of anaerobically stabilized sludge. A mandatory characterization of ISO SS isolated strains from anaerobic stabilized sludge was performed in the process of identifying bacterial species. The cationic clay-based nanomaterial showed appreciable antibacterial activity against ISO SS, a Gram-negative bacterium. It also showed good activity against E. coli bacteria. As a catalyst in the catalytic ozonation of MG dye, BN-Ag⁰ significantly improves the oxidation time of the dye, due to its good adsorption and catalytic properties. The catalytic and antibacterial activities of the natural bentonite (BN) and of BN-Ag⁰ were examined using performant characterization techniques. The lifetime of the BN-Ag⁰ catalyst was also evaluated. Results obtained are expected to provide valuable findings for the preparation of a good microporous material with multiple functionalities.     

Ligand-enabled oxidation of gold(i) complexes with o-quinones

Chelating P^P and hemilabile P^N ligands were found to trigger the oxidation of Au(i) complexes by o-benzoquinones. The ensuing Au(iii) catecholate complexes have been characterized by NMR spectroscopy, single crystal X-ray diffraction and X-ray absorption spectroscopy. They adopt tetracoordinate square-planar structures. Reactivity studies substantiate the reversibility of the transformation. In particular, the addition of competing ligands such as chloride and alkenes gives back Au(i) complexes with concomitant release of the o-quinone. DFT calculations provide insight about the structure and relative stability of the Au(i) o-quinone and Au(iii) catecholate forms, and shed light on the 2-electron transfer from gold to the o-quinone.

Chelating P^P and hemilabile P^N ligands were found to trigger the oxidation of Au(i) complexes by o-benzoquinones.