Air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes: highly active initiators for living polymerization of isocyanides.

A family of air-stable (phenylbuta-1,3-diynyl)palladium(II) complexes were designed and prepared in a facile synthetic procedure. Their structures were characterized by (1)H and (13)C NMR, MS, and X-ray analysis. These Pd complexes were revealed to efficiently initiate the polymerization of phenyl isocyanides in a living/controlled chain growth manner, which led to the formation of poly(phenyl isocyanide)s with controlled molecular weights and narrow molecular weight distributions. (13)C NMR analysis indicated the isolated poly(phenyl isocyanide) was of high stereoregularity. The Pd unit at the end of the polymer chain could undergo further copolymerization with phenyl isocyanide monomers to give block copolymers. It was also found that incorporation of an electron-donating group on the phenyl group of the Pd complex could improve the catalytic activities. Furthermore, these Pd complexes were tolerant to most organic solvents and applicable to a wide range of isocyanide monomers including alkyl and phenyl isocyanides and even phenyl isocyanide with bulky substituents at the ortho position and diisocyanide monomers. Therefore, this polymerization system is versatile in the preparation of well-defined polyisocyanides with controlled sequence. Bi- and trifunctional Pd complexes with two and three Pd units incorporated onto the same phenyl ring were designed and synthesized. They were also able to initiate the living polymerization of phenyl isocyanide to afford telechelic linear and star-shaped polyisocyanides with controlled molecular weights and narrow molecular weight distributions.

Industrial-scale extraction of high value-added kaolin from excavation waste: Demonstration from Xiamen, China.

Excavation waste from the construction of subways and other underground infrastructures is mainly composed of gravel, sand and clay of minimal economic value, which commonly ends up in landfills. Although the coarse sand and gravel of the excavation waste are typically recycled on site, a large amount of the fine-grained residue must be disposed of due to the prohibition of marine land reclamation in Xiamen, China, leading to an increasingly severe shortage of landfills. In this contribution, a new strategy was successfully developed for industrial-scale extraction of high value-added kaolin from the excavation waste of Xiamen. This strategy can overcome the challenges of complex and variable chemical compositions, high iron contents, low industrial grade, and organic contaminants in the raw materials. Characterization using chemical analysis, powder X-ray diffraction, scanning electron microscopy, and infrared spectroscopy showed that the Xiamen excavation waste originated from granite weathering is mainly composed of kaolinite and quartz, along with high Fe contents and other impurities. The excavation waste was subjected to an intensive process of blunging, grinding, sieving, and classifying, as well as successive iron removal by magnetic separation. Subsequently, the extracted products meet commercial requirements, including those for high-quality kaolin with whiteness and plasticity larger than 90° and 17%, respectively. Moreover, an industrial-scale green production line with an annual treatment capacity of one million tonnes of excavation waste at the utilization rate of 100% was implemented. Hence, this work presents an effective approach for exploiting similar excavation waste around the world to promote sustainable development.

[Effects of different fertilization modes on paddy field topsoil organic carbon content and carbon sequestration duration in South China].

Based on the organic carbon data of 222 topsoil samples taken from 38 paddy field experiment sites in South China, calculations were made on the relative annual change of topsoil organic carbon content (RAC) and carbon sequestration duration in the paddy fields in South China under five fertilization modes (inorganic nitrogen fertilization, N; inorganic nitrogen and phosphorus fertilization, NP; inorganic nitrogen, phosphorus, and potassium fertilization, NPK; organic fertilization, O; and inorganic plus organic fertilization, OF). The RAC under the fertilizations was 0-0.4 g x kg(-1) x a(-1), with an increment of 0.20 and 0.26 g x kg(-1) x a(-1) in double and triple cropping systems, respectively. The RAC was higher in treatments O and OF than in treatments N, NP, and NPK, being the highest (0.32 g x kg(-1) x a(-1)) in treatment OF. The topsoil organic carbon accumulation rate decreased with increasing time, and the carbon sequestration duration in treatments N, NP, NPK, O, and OF was about 22, 28, 38, 57, and 54 years, respectively. Inorganic plus organic fertilization was the most effective practice for soil carbon sequestration in the paddy fields in South China.