Nickel-4'-(3,5-dicarboxyphenyl)-2,2',6',2″-terpyridine Framework: Efficient Separation of Ethylene from Acetylene/Ethylene Mixtures with a High Productivity.

A novel compound, [Ni(DCPTP)] n (termed Ni-DCPTP), based on the 4'-(3,5-dicarboxyphenyl)-2,2',6',2″-terpyridine (DCPTP2-) ligand was presented here. Ni-DCPTP has a three-dimensional structure with a ths topology featuring one-dimensional (1D) helical channels. Ni-DCPTP shows an efficient removal of a trace amount of C2H2 from a C2H2/C2H4 (1/99) mixture with an excellent C2H4 productivity as demonstrated by both the transient breakthrough simulations and breakthrough experiments, generating the polymer-grade C2H4 gas (C2H2 < 40 ppm). The carboxylate oxygen atoms on the surface of 1D channels are the preferential binding sites for C2H2 molecules. This work demonstrates an elegant example with carboxylate oxygen-functionalized pore channels for effective C2H2/C2H4 separation.

Nanocomposite films based on xylan-rich hemicelluloses and cellulose nanofibers with enhanced mechanical properties.

Interest in xylan-rich hemicelluloses (XH) film is growing, and efforts have been made to prepare XH films with improved mechanical properties. This work described an effective approach to produce nanocomposite films with enhanced mechanical properties by incorporation of cellulose nanofibers (CNFs) into XH. Aqueous dispersions of XH (64-75 wt %), sorbitol (16-25 wt %), and CNF (0-20 wt %) were cast at a temperature of 23 °C and 50% relative humidity. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermal analysis (TG) and X-ray diffraction (XRD). The surface of XH films with and without CNF was composed primarily of nanonodules, and CNFs were embedded in the XH matrix. Freeze-dried XH powder was amorphous, whereas the films with and without CNF showed a distinct peak at around 2θ = 18°, which suggested that XH molecules aggregated or reordered in the casting solution or during water evaporation. Furthermore, the nanocomposite films had improved thermal stability. XH film with 25 wt % plasticizer (sorbitol, based on dry XH weight) showed poor mechanical properties, whereas incorporation of CNF (5-20 wt %, based on the total dry mixture) into the film resulted in enhanced mechanical properties due to the high aspect ratio and mechanical strength of CNF and strong interactions between CNF and XH matrix. This effective method makes it possible to produce hemicellulose-based biomaterials of high quality.

Homogeneous esterification of xylan-rich hemicelluloses with maleic anhydride in ionic liquid.

Generation of bioenergy, new functional polymers, or chemicals and biomaterials from hemicelluloses are important uses for biomass. In this paper, a novel functional biopolymer with carbon-carbon double bond and carboxyl groups was prepared by a homogeneous esterification of xylan-rich hemicelluloses (XH) with maleic anhydride in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid using LiOH as catalyst. The biopolymers with degrees of substitution (DS) between 0.095 and 0.75 were accessible in a completely homogeneous system by changing reaction temperature, reaction time, the dosage of catalyst, and the molar ratio of maleic anhydride to anhydroxylose unit in XH. Results obtained from FT-IR and (13)C NMR spectroscopies confirmed the structure of hemicellulosic derivatives with carbon-carbon double bond and carboxyl groups, implying an efficient method to prepare a novel and important functional biopolymer for biomaterials.

Long-chain anhydride modification: a new strategy for preparing xylan films.

Xylan, which is a widely abundant plant polymer, has been considered as an alternative for film preparation. Up to now, however, xylan films have suffered from brittleness, low mechanical strength, and humidity sensitivity. This paper describes a new and effective strategy to prepare xylan films with high mechanical strength and less moisture-sensitive properties by introducing long carbon chains into the xylan backbone. Furthermore, this work revealed some important details on the relationships between structure (molecular structure, aggregation behaviors, and surface morphology) and properties (film-forming performance, flexibility, tensile strength, and hydrophilicity) of xylan film. It was found that the hydrophobic carbon chains (2-octenylsuccinic anhydride half-ester groups) in the xylan backbone acted as steric hindrance and could effectively prevent xylan chains from aggregation. 2-Octenylsuccinic anhydride (2-OSA) modified xylan (2-OSA-X) demonstrated amorphous structure and had better film-forming performance than the unmodified xylan. 2-OSA-X films were smooth, flexible, and less moisture-sensitive and showed significantly increasing tensile strength at a low degree of substitution.

Synthesis and characterization of amphoteric xylan-type hemicelluloses by microwave irradiation.

In this study, a novel amphoteric macromolecule was synthesized by sequential incorporation of carboxymethyl and quaternary ammonium groups into the backbone of xylan-type hemicelluloses under microwave irradiation. The reaction parameters such as the molar ratio of reagent (NaOH or 3-epoxypropyltrimethylammonium chloride)/anhydroxylose unit in hemicelluloses, the temperature, and the reaction time were investigated to optimize the reaction condition. The maximum degrees of substitution (DS) of carboxymethyl and quaternary ammonium groups under the optimum reaction condition were 0.90 and 0.52, respectively, exhibiting a higher efficiency as compared to the conventional heating method. Moreover, the thermal stability and weight-average molecular weight of amphoteric hemicellulosic derivatives decreased as compared to the native hemicelluloses. The viscosity, elastic modulus, and loss modulus of the amphoteric biomacromolecules increased with the increasing DS of quaternary ammonium groups in aqueous solution due to stronger electrostatic attraction. This study provides an efficient and rapid method to prepare amphoteric biomacromolecules.

Highly effective adsorption of heavy metal ions from aqueous solutions by macroporous xylan-rich hemicelluloses-based hydrogel.

Xylan-rich hemicelluloses-based hydrogel was developed as a novel porous bioadsorbent by graft co-polymerization of acrylic acid (AA) and xylan-rich hemicelluloses for adsorption of heavy metal ions (Pd(2+), Cd(2+), and Zn(2+)) from aqueous solutions. The chemical structure, the interaction between the hydrogel and metal ions, and the porous structure of xylan-rich hemicelluloses-g-AA hydrogel were revealed by Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of AA and cross-linker dosage, pH value, contacting time, and initial concentration of metal ion on the adsorption capacity were studied. The adsorption equilibrium time was about 60 min from the adsorption kinetics study. The maximum adsorption capacities of Pd(2+), Cd(2+), and Zn(2+) were 859, 495, and 274 mg/g, respectively. Furthermore, xylan-rich hemicelluloses-g-AA hydrogel also exhibited highly efficient regeneration and metal ion recovery efficiency and can be reused without noticeable loss of adsorption capacity for Pd(2+), Cd(2+), and Zn(2+) after quite a number of repeated adsorption/desorption cycles.

Adsorption of heavy metals by a porous bioadsorbent from lignocellulosic biomass reconstructed in an ionic liquid.

A novel porous bioadsorbent for metal ion binding (Pd(2+) and Cd(2+)) was successfully prepared from lignocellulosic biomass in ionic liquid by homogeneous succinoylation and sequent chemical cross-linking. The morphology of the bioadsorbent and the interaction between bioadsorbent and metal ions was revealed by scanning electron microscopy and Fourier transform infrared spectroscopy. Results showed that the adsorption mechanism of the bioadsorbent was an ion exchange. A lower dose of cross-linker or higher carboxyl content increased the adsorption capacities of Pd(2+) and Cd(2+). The adsorption capacities of Pd(2+) and Cd(2+) remarkably increased as the pH of metal ion solutions increased. The pores in the bioadsorbent greatly favored the diffusion and adsorption of metal ions, and the adsorption equilibrium time was about 50 min. The adsorption of metal ions could be well explained by the Langmuir model, and the maximum adsorption capacities of Pd(2+) and Cd(2+) were 381.7 and 278.6 mg/g.

Microwave-induced synthesis of carboxymethyl hemicelluloses and their rheological properties.

In this article, a facile, rapid, and efficient method was developed for the preparation of carboxymethyl hemicelluloses using microwave-induced organic reaction enhancement chemistry. The influences of the factors including reaction time, temperature, and the amount of sodium monochloroacetate and sodium hydroxide on the degree of substitution (DS) of the products were investigated. The rheological properties and the chemical structure of the resulting polymers were also studied. It was found that microwave irradiation could significantly promote the chemical reaction efficiency and accelerate the carboxymethylation of hemicelluloses with sodium monochloroacetate. Therefore, carboxymethyl hemicelluloses with higher DS of 1.02 could be obtained in much shorter time scales as compared to the conventional heating method. Results from rheological analysis indicated that carboxymethyl hemicellulose solutions exhibited shear-thinning behavior in the range of shear rates tested and showed lower viscosity and modulus in comparison with those of the native hemicelluloses due to lower molecular weight and the role of carboxymethyl groups in reducing the entanglements between hemicelluloses chains.

Xylan-rich hemicelluloses-graft-acrylic acid ionic hydrogels with rapid responses to pH, salt, and organic solvents.

Exploitation of biomaterials derived from renewable resources is an important approach to address environmental and resource problems in the world today. In this paper, novel ionic hydrogels based on xylan-rich hemicelluloses were prepared by free radical graft copolymerization of acrylic acid (AA) and xylan-rich hemicelluloses (XH) by using N,N-methylene-bis(acrylamide) (MBA) as cross-linker and ammonium persulfate/N,N,N',N'-tetramethylethylenediamine (APS/TMEDA) as redox initiator system. The network characteristics of the ionic hydrogels were investigated by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), as well as by determination of mechanical properties, swelling, and stimuli responses to pH, salts, and organic solvents. The results showed that an increase in the MBA/XH or AA/XH ratio resulted in higher cross-linking density of the network and thus decreased the swelling ratio. Expansion of the network hydrogels took place at high pH, whereas shrinkage occurred at low pH or in salt solutions as well as in organic solvents. The ionic hydrogels had high water adsorption capacity and showed rapid and multiple responses to pH, ions, and organic solvents, which may allow their use in several areas such as adsorption, separation, and drug release systems.