Preparation of a silver nanoparticle-based dual-functional sensor using a complexation-reduction method.

A dual-functional sensor based on silver nanoparticles was synthesized by a two-stage procedure consisting of a low-temperature chitosan-Ag(+) complexation followed by a high-temperature reduction of the complex to form chitosan-capped silver nanoparticles (CS-capped Ag NPs). The surface plasmon resonance (SPR) absorption and fluorescence emission of the silver nanoparticles were influenced by the concentration and degradation time of chitosan, and the temperatures of the complexation and reduction reactions. The SPR absorption band was blue-shifted while the intensities of emission and absorption were decreased after reacting the silver nanoparticles with Hg(2+) ions. The silver nanoparticles reacted with Hg(2+) were characterized by high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and surface-enhanced Raman scattering spectroscopy (SERS). The results suggested that the particle growth and aggregation of the silver nanoparticles were caused by the adsorption of Hg(2+) and deposition of Hg(0) on the nanoparticle surface. Direct correlations of the SPR absorption and fluorescence emission with the concentration of Hg(2+) were useful for quantitative analysis of Hg(2+). It was possible to use the dual-functional silver nanoparticles as a colorimetric and fluorescent sensor for sensitive and selective detection of Hg(2+) ions.

Delivery of berberine using chitosan/fucoidan-taurine conjugate nanoparticles for treatment of defective intestinal epithelial tight junction barrier.

Bacterial-derived lipopolysaccharides (LPS) can cause defective intestinal barrier function and play an important role in the development of inflammatory bowel disease. In this study, a nanocarrier based on chitosan and fucoidan was developed for oral delivery of berberine (Ber). A sulfonated fucoidan, fucoidan-taurine (FD-Tau) conjugate, was synthesized and characterized by Fourier transform infrared (FTIR) spectroscopy. The FD-Tau conjugate was self-assembled with berberine and chitosan (CS) to form Ber-loaded CS/FD-Tau complex nanoparticles with high drug loading efficiency. Berberine release from the nanoparticles had fast release in simulated intestinal fluid (SIF, pH 7.4), while the release was slow in simulated gastric fluid (SGF, pH 2.0). The effect of the berberine-loaded nanoparticles in protecting intestinal tight-junction barrier function against nitric oxide and inflammatory cytokines released from LPS-stimulated macrophage was evaluated by determining the transepithelial electrical resistance (TEER) and paracellular permeability of a model macromolecule fluorescein isothiocyanate-dextran (FITC-dextran) in a Caco-2 cells/RAW264.7 cells co-culture system. Inhibition of redistribution of tight junction ZO-1 protein by the nanoparticles was visualized using confocal laser scanning microscopy (CLSM). The results suggest that the nanoparticles may be useful for local delivery of berberine to ameliorate LPS-induced intestinal epithelia tight junction disruption, and that the released berberine can restore barrier function in inflammatory and injured intestinal epithelial.

Sequential removal of phosphate and copper(II) ions using sustainable chitosan biosorbent.

Although adsorbents are good candidates for removing phosphorus and heavy metals from wastewater, the use of biosorbents for the sequential treatment of phosphorus and copper has not yet been studied. Porous chitosan (CS)-based biosorbents (CGBs) were developed to adsorb phytic acid (PA), a major form of organic phosphate. This first adsorbate (PA) further served as an additional ligand (P-type ligand) for the CGBs (N-type ligand) to form a complex with the second adsorbate (copper). After the adsorption of PA (the first adsorbate), the spent CGBs were recycled and used as a new adsorbent to adsorb Cu(II) ions (the second adsorbate), which was expected to have a dual coordination effect through P, N-ligand complexation with copper. The interactions and complexation between CS, PA and Cu(II) ions on the PA-adsorbed CGBs (PACGBs) were investigated by performing FTIR, XPS, XRD, and SEM-EDS analyses. The PACGBs exhibited fast and enhanced adsorption of Cu(II) ions, owing to the synergistic effect of the amino groups of CS (the original ligand, N-type) and the phosphate groups of PA (an additional ligand, P-type) on the adsorption of Cu(II) ions. This is the first time that sequential removal of phosphorus and heavy metals by biosorbents has been performed using biosorbents.

Tripolyphosphate cross-linked macromolecular composites for the growth of shape- and size-controlled apatites.

Bioactive composites that enable the formation of calcium phosphates have received increased attention over the last decade, in the development of osteoconductive biomaterials for orthopaedic applications. In this work, tripolyphosphate (TPP)-cross-linked chitosan/gelatin composites (TPP-CG) were prepared for the growth of shape- and size-controlled calcium phosphates on/in the composites. The mineralization pattern of the composites, after soaking in the Ca(OH)(2) aqueous solution, clearly demonstrated oriented, needle-like nanocrystallites of calcium phosphates in the matrix with especially high Ca/P molar ratio (3.98) as detected by energy dispersive X-ray spectroscopy (EDX) analysis. Subsequent to mineralization in a simulated body fluid (SBF), the mineralized composites showed micro-scaled spherical aggregates deposited on the surface and granule-like nanocrystallites grew in the matrix. The Ca/P molar ratio (1.72) and X-ray diffraction pattern of the nanocrystallites grown in the composites were similar to those of hydroxyapatite (HAp). Osteoblastic differentiation of ROS cells cultured on the mineralized composites allowed an enhanced expression of the chosen osteogenic marker (alkaline phosphatase, ALPase). These results indicated that the composites mineralized with micro- and nano-scaled calcium phosphates with various structural features make them attractive for bone tissue engineering applications.

Filling-Balance-Oriented Parameters for Multi-Cavity Molds in Polyvinyl Chloride Injection Molding.

PVC injection molding has constrained temperature and shear rate owing to its temperature sensitivity and high viscosity, as well as its low conductivity. Many challenges are associated with the PVC injection molding process used for producing PVC fittings with a multi-cavity mold. Once filling imbalance occurs, the gates and/or runner of the mold should be changed by machine tools, which is time- and cost-intensive. Using Moldex3D and the Taguchi method, this study reveals an approach to eliminate imbalanced filling of multi-cavity molds for PVC injection molding. The injection rate optimization of the filling stage is successfully verified to reduce the imbalance. Furthermore, the temperatures of the molded PVC fittings are only slightly increased by the change in injection rate. The temperatures of fittings in the filling and packing are lower than the degradation temperature of PVC. This approach may help technicians to obtain pilot-run samples for the optimization of molding parameters and ensure degradation-free PVC molding.

Feasibility Study on the Fused Filaments of Injection-Molding-Grade Poly(Ethylene Terephthalate) for 3D Printing.

Unlike that of glycol-modified Poly(ethylene terephthalate) (PETG), the crystallinity of PET can be post-adjusted to enhance the mechanical properties of 3D-printed parts such as food-contact tableware and bio-implants. The aforementioned PET material could be 3D printed to produce the desired parts for performance evaluation before mass production by injection molding. In this study, using differential scanning calorimetry (DSC), we examined the pellets, extruded filament, and printed specimen to identify variations in melting and crystalline temperatures, as well as crystallinity. It was also shown by Thermogravimetric Analyzer (TGA) that the addition of talcum powder increased the thermal stability of filament and resulted in an interaction between the fillers and polymer matrix. The crystallinities of the filament and printed specimen were then compared with the yield strengths and Young's moduli to confirm the effects of the decreased molecular weight of the extruded PET filament. The talcum powder effectively improved the viscosity of the PET melted during the extrusion process for the filament and then enhanced the crystallinity of the PET, thereby achieving a significantly higher Young's modulus. The printed PET specimen presented an excellent yield strength of 25 MPa and ductile properties with strain-at-break values of 30%, successfully indicating potential applications in food-contact tableware and bio-implants.

Thiol-modified chitosan sulfate nanoparticles for protection and release of basic fibroblast growth factor.

A series of chitosan (CS) derivatives, the 6-O-carboxymethylchitosan (6-O-CC), 2-N sulfated 6-O-carboxymethylchitosan (N-SOCC) and the 2-N and 3,6-O sulfated 6-O-carboxymethyl chitosan (N,O-SOCC) were synthesized in this study. The chemical structures and the degrees of substituted carboxymethyl and sulfate groups of the synthesized compounds were respectively determined by FT-IR spectra and elemental analysis. N,O-SOCC displayed the highest protective efficiency for basic fibroblast growth factor (bFGF) as examined by the L929 fibroblast culture test and docking simulation. N,O-SOCC-4-thio-butylamidine (TBA) conjugates prepared by modification of N,O-SOCC with 2-iminothiolane were in situ cross-linkable. The degrees of thiol substitution of the 2-iminothiolane modified N,O-SOCC polymers were determined to be in the ranges of 45.9 +/- 3.7 and 415.6 +/- 12.5 micromol SH/g SOCC by quantifying the amount of thiol groups on the thiolated polymers with Ellman's reagent. The 2-iminothiolane modified N,O-SOCC and CS complex could be used for preparing nanoparticles by a polyelectrolyte self-assembly method, and the release of bFGF from the nanoparticles was successfully controlled. L929 fibroblast culture tests showed that the thiol modified N,O-SOCC/CS nanoparticles could effectively protect bFGF from inactivation over a 120 h period. The results of this study suggest that the thiol modified N,O-SOCC/CS nanoparticles may be useful as novel materials for specific delivery of bFGF with mitogenic activity.

Mutlifunctional nanoparticles prepared from arginine-modified chitosan and thiolated fucoidan for oral delivery of hydrophobic and hydrophilic drugs.

Self-assembled nanoparticles (NPs) from arginine-modified chitosan (CS-N-Arg) and thiolated fucoidan (THL-fucoidan) were synthesized to enhance the transport of dextran and curcumin across intestinal epithelial cell layer. CS-N-Arg/THL-fucoidan NPs exhibited a pH-sensitive assembly-disassembly and drug release property. Evaluations of the NPs in enhancing the transport of a hydrophilic macromolecule (FITC-dextran) and a hydrophobic drug (curcumin) were investigated in Caco-2 cell monolayers. The cationic CS-N-Arg in the NPs induced disruption of intestinal epithelial tight junctions as indicated by the decrease of transepithelial electrical resistance (TEER). Permeation studies revealed that the NPs enhanced the paracellular permeation of macromolecular dextran through the monolayer barrier. In addition, the multifunctional NPs increased the permeability of rhodamine 123 because the thiomer THL-fucoidan in the NPs inhibited P-glycoprotein. Cellular uptake and permeability of curcumin encapsulated in the NPs were improved due to increasing their water solubility and stability.

Adsorption of copper(II) ions by a chitosan-oxalate complex biosorbent.

Oxalic acid, an effective metal-chelating ligand, is abundant in natural resources. In this study, a chitosan-oxalate complex biosorbent (COCB) was prepared by an iontropic cross-linking method. The COCB beads were characterized by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The XRD analysis shows that Cu(II) ions can form complexes with chitosan and oxalate. Adsorption of Cu(II) ions onto COCB beads was pH-dependent. The isothermal adsorption data fitted well to Langmuir equation with the maximum adsorption capacities of 227.27 mg/g for porous COCB beads and 175.44 mg/g for non-porous COCB beads at pH 5.0. The adsorption kinetics described by the pseudo-second-order diffusion models, suggesting that the rate-limiting step in adsorption was chemical sorption. Thermodynamic parameters (ΔG°<0 and ΔH°>0) indicated a spontaneous and endothermic adsorption process. The COCB bioadsorbent exhibited fast adsorption rate and high adsorption capacity for Cu(II) uptake.

Combination of carboxymethyl chitosan-coated magnetic nanoparticles and chitosan-citrate complex gel beads as a novel magnetic adsorbent.

Magnetic chitosan beads were synthesized by incorporating N,O-carboxymethyl chitosan-coated magnetic nanoparticles (NOCC-MNPs) into chitosan-citrate gel beads (CCGBs) for adsorbing Cu(II) ions. An increase of Cu(II) adsorption capacity was due to the combined chelation effects from the electron-donating functional groups in the CCGBs and NOCC-MNPs. Moreover, the paramagnetic susceptibility of Cu(II) citrate chelates could further improve the Cu(II) adsorption efficiency through the force of magnetic attraction. The adsorption data of the magnetic CCGBs fitted well with the Freundlich model, whereas the adsorption kinetics followed the pseudo-second-order kinetic model. The maximal adsorption capacity as estimated by the Langmuir model was 294.11mg/g. The adsorption thermodynamic parameters indicated that the involved process should be spontaneous and exothermic.

Effect of tannic acid-fish scale gelatin hydrolysate hybrid nanoparticles on intestinal barrier function and α-amylase activity.

Practical application of tannic acid is limited because it readily binds proteins to form insoluble aggregates. In this study, tannic acid was self-assembled with fish scale gelatin hydrolysates (FSGH) to form stable colloidal complex nanoparticles. The nanoparticles prepared from 4 mg ml(-1) tannic acid and 4 mg ml(-1) FSGH had a mean particle size of 260.8 ± 3.6 nm, and showed a positive zeta potential (20.4 ± 0.4 mV). The nanoparticles acted as effective nano-biochelators and free radical scavengers because they provided a large number of adsorption sites for interaction with heavy metal ions and scavenging free radicals. The maximum adsorption capacity for Cu(2+) ions was 123.5 mg g(-1) and EC50 of DPPH radical scavenging activity was 21.6 ± 1.2 µg ml(-1). Hydroxyl radical scavenging effects of the nanoparticles were investigated by electron spin resonance spectroscopy. The copper-chelating capacity and free radical scavenging activity of the nanoparticles were associated with their capacity to inhibit Cu(2+) ion-induced barrier impairment and hyperpermeability of Caco-2 intestinal epithelial tight junction (TJ). However, α-amylase inhibitory activity of the nanoparticles was significantly lower than that of free tannic acid. The results suggest that the nanoparticles can ameliorate Cu(2+) ion induced intestinal epithelial TJ dysfunction without severely inhibiting the activity of the digestive enzymes.

Preparation of fucoidan-shelled and genipin-crosslinked chitosan beads for antibacterial application.

In this study, a fucoidan-shelled chitosan bead was developed with the purpose of oral delivery of berberine to inhibit the growth of bacteria. The cross-linking level and swelling property of the beads were affected by the pH value and the composition of the genipin/fucoidan combined gelling agent. The drug release of the berberine-loaded beads was faster in simulated gastric fluid (pH 1.2) than those in simulated intestinal fluid (pH 7.4). Furthermore, a nanoparticles/beads complex system was developed by incorporation of berberine-loaded chitosan/fucoidan nanoparticles in the fucoidan-shelled chitosan beads. The nanoparticles/beads complex served as a drug carrier to delay the berberine release in simulated gastric fluid, with an estimated lag time of 2 h. Our results showed that the berberine-loaded beads and nanoparticles/beads complex could effectively inhibit the growth inhibition of common clinical pathogens, such as Staphylococcus aureus and Escherichia coli, and have the advantage of continually releasing berberine to inhibit the growth of the bacteria over 24 h.

Stimuli-responsive materials prepared from carboxymethyl chitosan and poly(γ-glutamic acid) for protein delivery.

The development of stimuli-responsive materials in response to the molecules involved in biological processes has gained increased attentions. In this work, carboxymethyl chitosan (CM-chitosan) and poly(γ-glutamic acid) (pGlu) were reacted with a naturally occurring compound, genipin, leading to the formation of genipin-crosslinked CM-chitosan/pGlu conjugates with fluorescence emissions. The genipin-conjugated polymers were sensitive to the oxidation product of glucose, gluconic acid and hydrogen peroxide (H2O2). Fluorescence emissions of the polymers were quenched by gluconic acid and H2O2. An increase in the hydrodynamic diameter together with the quenching of fluorescence indicated that the genipin-conjugated polymers were self-aggregated into nanoparticles, in response to the stimulus of gluconic acid (but not for H2O2). Bovine serum albumin (BSA) could be loaded in the self-aggregated nanoparticles, and the incorporated BSA slowly released from the nanoparticles under hyper-gluconic acid conditions. This material is hence proposed as a stimuli-responsive material for optical sensing and protein delivery purposes.

Characteristics of microporous/mesoporous carbons prepared from rice husk under base- and acid-treated conditions.

The study reports the preparation of activated carbon with a high surface area from rice husk using chemical activation with H(3)PO(4) and ZnCl(2). Activated carbon prepared from rice husk usually exhibits low specific surface areas due to its high ash content. However, experimental results show that base-leaching and acid-washing processes can effectively enhance the adsorption capacity of rice-husk carbon. The study also investigates the effects of preparation parameters on the surface characteristics of the carbon. These parameters include the kind of activating agent, before and after treatment procedures, impregnation ratio and activation temperature. The chemical and physical properties of samples were examined by EA, ICP-MS, XRD, FTIR, SEM and a N(2)-adsorption meter. The surface areas obtained from ZnCl(2) and H(3)PO(4) activation are as high as 2434 and 1741 m(2)/g, respectively. These values are higher than that of activated carbon treated with neither base nor acid (1262 and 508 m(2)/g for ZnCl(2) and H(3)PO(4) activation). Thermogravimetric analysis shows that the activation process can be divided into three parts based on temperature zones. The results of this study will be useful in developing resource recovery systems for agricultural biomass.

Synthesis of zero-valent copper-chitosan nanocomposites and their application for treatment of hexavalent chromium.

This study used ionotropic crosslinking to synthesize chitosan-tripolyphosphate chelating resin beads, which are used to fabricate zero-valent copper-chitosan nanocomposites. The copper nanoparticles were dispersed on chitosan-tripolyphosphate beads, and were thus able to maintain appropriate dispersion and stability, which greatly improves their applicability. The fabrication process contains two steps: using chitosan-tripolyphosphate beads to adsorb Cu(II) ions, followed by chemical reduction to reduce Cu(II) ions to zero-valent copper. This study explored the adsorption of synthesized chitosan-tripolyphosphate beads to Cu(II) ions, and used SEM/EDS, XPS, and TEM to examine the properties of zero-valent copper-chitosan nanocomposites. The results showed that, the adsorption behavior of hexavalent chromium from aqueous solution onto fabricated nanocomposites has better adsorption capacity than that of the chitosan-tripolyphosphate beads.