Self-assembly of copper sulfate and a poly(imidazole-acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO(4) via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO(4) to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5-45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h(-1), respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

Metalloenzymes are essential proteins with vital activity that promote high-efficiency enzymatic reactions. To ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, it is important to develop metalloenzyme-inspired polymer-supported metal catalysts. Here, we present a highly active, reusable, self-assembled catalyst of poly(imidazole-acrylamide) and palladium species inspired by metalloenzymes and apply our convolution methodology to the preparation of polymeric metal catalysts. Thus, a metalloenzyme-inspired polymeric imidazole Pd catalyst (MEPI-Pd) was readily prepared by the coordinative convolution of (NH(4))(2)PdCl(4) and poly[(N-vinylimidazole)-co-(N-isopropylacrylamide)(5)] in a methanol-water solution at 80 °C for 30 min. SEM observation revealed that MEPI-Pd has a globular-aggregated, self-assembled structure. TEM observation and XPS and EDX analyses indicated that PdCl(2) and Pd(0) nanoparticles were uniformly dispersed in MEPI-Pd. MEPI-Pd was utilized for the allylic arylation/alkenylation/vinylation of allylic esters and carbonates with aryl/alkenylboronic acids, vinylboronic acid esters, and tetraaryl borates. Even 0.8-40 mol ppm Pd of MEPI-Pd efficiently promoted allylic arylation/alkenylation/vinylation in alcohol and/or water with a catalytic turnover number (TON) of 20,000-1,250,000. Furthermore, MEPI-Pd efficiently promoted the Suzuki-Miyaura reaction of a variety of inactivated aryl chlorides as well as aryl bromides and iodides in water with a TON of up to 3,570,000. MEPI-Pd was reused for the allylic arylation and Suzuki-Miyaura reaction of an aryl chloride without loss of catalytic activity.

Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

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A waste material known as palm oil empty fruit bunch (EFB) is used as a source of cellulose for the development of polymeric materials for the removal of metal ions from industrial wastewater. A poly(acrylonitrile)-grafted palm cellulose copolymer was synthesized by a conventional free radical initiating process followed by synthesis of a poly(amidoxime) ligand by oximation reaction. The resulting products were characterized by FT-IR, FE-SEM, EDX, TGA, DSC, and XPS. The poly(amidoxime) ligand was used to coordinate with and extract a series of transition metal ions from water samples. The binding capacity (qe) of the ligand with the metal ions such as copper, iron, cobalt, nickel, and lead were 260, 210, 168, 172, and 272 mg g−1 , respectively at pH 6. The adsorption process followed the pseudo-first-order kinetic model (R2 > 0.99) and as well as the Freundlich isotherm model (R2 > 0.99) indicating the occurrence of a multi-layer adsorption process in the amidoxime ligand adsorbent. Results from reusability studies show that the ligand can be recycled for at least 10 cycles without any significant losses to its initial adsorption capacity. The synthesized polymeric ligand was shown to absorb heavy metals from electroplating wastewater with up to 95% efficiency.

A broad peak of the reflectance spectra at 700 nm was created when Cu(ii) ions (6 to 18 ppm) is adsorbed by ligand whereas blank polymeric ligand does not. Colour optimization of Cu(ii)-complex and HR-TEM micrograph are shown in figure inset.

The immobilized N-heterocyclic carbene-Pd complex was readily prepared by reaction of silica gel-supported imidazolium chloride with Pd(OAc) 2 . The Pd complex exhibited excellent catalytic activity in the coupling reaction of aryl halides with arylboronic acid. The heterogeneous Pd catalyst was reusable as well as air-stable to allow easy use.

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