Reutilization of discarded biomass for preparing functional polymer materials.

Biomass is abundant and recyclable on the earth, which has been assigned numerous roles to human beings. However, over the past decades, accompanying with the rapid expansion of man-made materials, such as alloy, plastic, synthetic rubber and fiber, a great number of natural materials had been neglected and abandoned, such as straw, which cause a waste of resource and environmental pollution. In this review, based on introducing sources of discarded biomass, the main composition and polymer chains in discarded biomass materials, the traditional treatment and novel approach for reutilization of discarded biomass were summarized. The discarded biomass mainly come from plant wastes generated in the process of agriculture and forestry production and manufacturing processes, animal wastes generated in the process of animal husbandry and fishery production as well as the residual wastes produced in the process of food processing and rural living garbage. Compared with the traditional treatment including burning, landfill, feeding and fertilizer, the novel approach for reutilization of discarded biomass principally allotted to energy, ecology and polymer materials. The prepared functional materials covered in composite materials, biopolymer based adsorbent and flocculant, carrier materials, energy materials, smart polymer materials for medical and other intelligent polymer materials, which can effectively serve the environmental management and human life, such as wastewater treatment, catalyst, new energy, tissue engineering, drug controlled release, and coating. To sum up, the renewable and biodegradable discarded biomass resources play a vital role in the sustainable development of human society, as well as will be put more emphases in the future.

Fabrication of dual-sensitive keratin-based polymer hydrogels and their controllable release behaviors.

Using feather keratin (FK) as a biocompatible and inexpensive biopolymer, a kind of dual-sensitive keratin-based polymer hydrogel (FK/PNiPA/PIAc-Gel) with interpenetrating network structure was prepared by two-step polymerization of N-isopropyl acrylamide (NiPA) and itaconic acid (IAc) in presence of crosslinker. After being characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis and scanning electron microscopy, its swelling behaviors and environmental sensitivity were investigated. The obtained biopolymer based hydrogel has good swelling and deswelling performance, and it is sensitive to pH value, temperature and salts of environment. Using anticancer drug, doxorubicin hydrochloride (Dox·HCl),  and Bovine serum albumin (BSA) as different drug molecules, its release behaviors in different environment were investigated. It was found that the release behaviors of FK/PNiPA/PIAc-Gel were controllable via adjusting pH value or temperature of environment. The cumulative release of the anticancer drug (Dox·HCl) reached 93.3% within 16 h, and the cumulative release rate of macromolecular drug (BSA) got to 75.9% in 24 h. In summary, the keratin-based biopolymer hydrogel with interpenetrating network structure, pH-sensitivity and temperature sensitivity are potentially applied to sustain drug carrier and humid medicinal material in the biomedical field or clinical nursing field.

Mechanisms on formation of hierarchically porous carbon and its adsorption behaviors.

Using simple one-step carbonization-activation, the residues of paulownia flowers are employed as a precursor to prepare hierarchically porous activated carbon. After investigating the optimum conditions, the obtained paulownia flowers based activated carbon (PFAC) is characterized by Fourier transform infrared spectroscopy, scanning electron microscope, transmission electron microscope, Brunauer-Emmett-Teller specific surface area analysis (S(BET)), thermo gravimetric analysis, and X-ray photoelectron spectroscopy. The PFAC owns a high specific surface area of 1,053 m(2)/g as well as a hierarchically porous structure with a combination of micro-, meso- and macropores. The pore-forming mechanism is discussed according to results of characterization. Using methylene blue as model dye, the adsorption behaviors of PFAC were investigated. We found that the dye could be rapidly adsorbed by hierarchically porous PFAC, and the adsorption capacity of PFAC reached 300 mg/g.

A facile fabrication of amphiphilic Janus and hollow latex particles by controlling multistage emulsion polymerization.

In this paper, we found that morphology controllable compound latex particles could be prepared by controlling the multistage emulsion polymerization. Influences of the content of methacrylic acid (MAA) on preparing the hydrophilic cores and the particles were investigated with the observation of dynamic light scattering (DLS) and transmission electron microscope (TEM) results. The acorn-like latex particles were synthesized by partially encapsulated with hydrophobic polystyrene (PSt)-layer. With adding moderate polarity polymethylmethacrylate (PMMA) interlayer, the hydrophilic cores could be fully encapsulated by the hydrophobic PSt-layer, and the core-shell structure formed. After alkali treatment, the acorn-like and core-shell latex particles evolved into amphiphilic Janus and hollow latex particles, respectively. The morphology of latex particles was investigated by TEM, and the forming mechanism of amphiphilic Janus and hollow latex particles was proposed.

Study on effective extraction of chicken feather keratins and their films for controlling drug release.

We report the fabrication of keratin films with porosity using keratin, for controlled drug delivery systems. Feathers are currently an important waste product from the poultry industry, however abandoned down products cause an environmentally difficult disposal problem as they are not efficiently extracted and applied. In this paper, feather keratin was extracted using a high-efficiency method. The yield of pure keratin was up to 90%. Its molecular weight was 20 kDa with low dispersity. The films, based on the extracted keratin, were prepared using a simple method, and showed good mechanical properties. Furthermore, the feather keratin films were used to load and release drugs. The resultant feather keratin biopolymer films were pH-responsive and showed controllable drug-release behavior. In summary, we achieved a simple method to reutilize disused feathers. It could be an attractive candidate for applications in the biomedical field.

Loess clay based copolymer for removing Pb(II) ions.

Functional monomers, such as acrylic acid and 2-hydroxyethyl methacrylate were supported into loess clay in situ polymerization, which afforded loess clay based copolymer (LC/PAAHM), a new kind of polymer adsorbent for removing Pb(II) ions from aqueous solution. Characterization of the polymer adsorbent was carried out by different sophisticated methods, such as Fourier transformation infrared spectrometry (FTIR), scanning electron microscopy (SEM), X-ray diffractometry (XRD), thermogravimetric analysis (TGA), and Zetasizer. Batch experiments were carried out to evaluate the factors affecting the removal efficiency, in which the pH, the adsorbent dosage, temperature and initial Pb(II) concentration all found in positive relevance to the increase of Pb(II) removal efficiency. The removal rate of Pb(II) got to 99% at room temperature and the adsorption capacity got to 356.9 mg/g. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data, and Langmuir and Freundlich models have been applied to study the adsorption equilibrium, respectively.

Photosensitized reduction of water to hydrogen using human serum albumin complexed with zinc-protoporphyrin IX.

We present the photophysical properties of complexes of recombinant human serum albumin (rHSA) with Zn(II)-protoporphyrin IX (ZnPP) and their activities in the photosensitized reduction of water to hydrogen (H2) using methyl viologen (MV2+) as an electron relay. The ZnPP is bound in subdomain IB of wild-type rHSA [rHSA(wt] by an axial coordination of Tyr-161 and, in the rHSA(I142H/Y161L) mutant [rHSA(His], by a His-142 coordination. Both the rHSA(wt)-ZnPP and rHSA(His)-ZnPP complexes showed a long-lived photoexcited triplet state with lifetimes (tauT) of 11 and 2.5 ms, respectively. The accommodation of ZnPP into the protein matrix efficiently eliminated the collisional triplet self-quenching process. The addition of a water-soluble electron acceptor, MV2+, resulted in a significant decrease in the triplet lifetime. The transition absorption spectrum revealed the oxidative quenching of rHSA-3ZnPP* by MV2+. The quenching rate constant (kq) and backward electron transfer rate constant (kb) were determined to be 1.4 x 10(7) and 4.7 x 10(8) M(-1) s(-1) for rHSA(wt)-ZnPP. In the presence of the colloidal PVA-Pt as a catalyst and triethanolamine (TEOA) as a sacrificial electron donor, the photosensitized reduction of water to H2 takes place. The efficiency of the photoproduction of H2 was greater than that of the system using the well-known organic chromophore, tetrakis(1-methylpyridinium-4-yl)porphinatozinc(II) (ZnTMPyP4+), under the same conditions.

Poly(ethylene glycol)-conjugated human serum albumin including iron porphyrins: surface modification improves the O2-transporting ability.

Artificial O2-carrying hemoprotein composed of human serum albumin including tetrakis(o-amidophenyl)porphinatoiron(II) (Fe4P or Fe3P) [HSA-FeXP] has been modified by maleimide- or succinimide-terminated poly(ethylene glycol) (PEG), and the formed PEG bioconjugates have been physicochemically characterized. 2-Iminothiolane (IMT) reacted with the amino groups of Lys to create active thiol groups, which bind to alpha-maleimide-omega-methoxy PEG [Mw: 2-kDa (PEG(M2)), 5-kDa (PEG(M5))]. On the other hand, alpha-succinimidyl-omega-methoxy PEG [Mw: 2-kDa (PEG(S2)), 5-kDa (PEG(S5))] directly binds to Lys residues. MALDI-TOF MS of the PEG-conjugated HSA-FeXP showed distinct molecular ion peaks, which provide an accurate number of the PEG chains. In the case of PEG(MY)(HSA-FeXP), the spectroscopic assay of the thiol groups also provided the mean of the binding numbers of the polymers, and the degree of the modification was controlled by the ratio of [IMT]/[HSA]. The viscosity and colloid osmotic pressures of the 2-kDa PEG conjugates (phosphate-buffered saline solution, [HSA] = 5 g dL(-1)) were almost the same as that of the nonmodified one, whereas the 5-kDa PEG binding increased the rheological parameters. The presence of flexible polymers on the HSA surface retarded the association reaction of O2 to FeXP and stabilized the oxygenated complex. Furthermore, PEG(MY)(HSA-FeXP) exhibited a long circulation lifetime of FeXP in rats (13-16 h). On the basis of these results, it can be concluded that the surface modification of HSA-FeXP by PEG has improved its comprehensive O2-transporting ability. In particular the PEG(MY)(HSA-FeXP) solution could be a promising material for entirely synthetic O2-carrying plasma expander as a red cell substitute.

Human serum albumin bearing covalently attached iron(II) porphyrins as O2-coordination sites.

Tetrakis{(alpha,alpha,alpha,alpha-o-pivalamido)phenyl}porphinatoiron(II) with a bifunctional tail possessing an axially coordinated imidazolyl group and a protein attachable succinimidyl(glutamyl) group (FeP-GluSu) has been synthesized. It can efficiently react with the lysine residues of recombinant human serum albumin (rHSA), giving a new albumin-heme conjugate [rHSA(FeP-Glu)]. MALDI-TOFMS showed a distinct molecular ion peak at m/z 70 643, which indicates that three FeP-Glu molecules were covalently linked to the rHSA scaffold. The binding number of FeP-Glu is approximately three (mol/mol) and independent of the mixing ratio. The CD spectrum and Native PAGE revealed that the albumin structure remained unaltered after the covalent bonding of the hemes. This rHSA(FeP-Glu) conjugate can bind and release O2 reversibly under physiological conditions (pH 7.3, 37 degrees C) in the same manner as hemoglobin and myoglobin. The O2-adduct complex had a remarkably long lifetime (tau(1/2): 5 h). The O2-binding affinity [P(1/2)O2: 27 Torr] was identical to that of human red cells. Laser flash photolysis experiments gave the O2- and CO-association rate constants and suggested that there are two different geometries of the imidazole binding to the central ion.