Electrospinning of chitosan/poly(lactic acid-co-glycolic acid)/hydroxyapatite composite nanofibrous mats for tissue engineering applications

Electrospinning, which is a fiber fabrication technique using electrical forces to produce fibers with diameters ranging from nanometers to several micrometers, can be used to prepare materials mimicking the extracellular matrix proteins for potential use as tissue engineering scaffolds. In this study, nanofibrous mats of chitosan (CH) and poly(lactic acid-co-glycolic acid) (PLGA) having fiber diameters between 167 to 525 nm, and containing hydroxyapatite (HAp), were prepared by electrospinning technique. Morphological, chemical, thermal and degradation tests and cell affinity tests were carried out. Chitosan mats were stable in aqueous media and showed degradability in the presence of lysozyme. In PBS solution, PLGA mats disintegrated completely in 2 weeks. Meanwhile, CH-PLGA mats containing equal amounts of both CH and PLGA fibers and CH-PLGA-HAp samples containing 20 % HAp lost 50 and 40 % of their initial weight in 4 weeks, respectively. Cell culture tests showed that all electrospun fibrous mats promoted SaOs-2 cell attachment and proliferation. However, cell proliferation on CH-PLGA-HAp fibrous mats was higher compared to the others after 7 days demonstrating the positive effect of HAp on cell affinity properties compared to pristine CH or PLGA fibrous scaffolds.     

Synthesis of EPDM-g-MAN by suspension graft copolymerization and its toughening effect on SAN resin

Suspension graft copolymerization of methyl methacrylate and acrylonitrile onto ethylene–propylene–diene terpolymer (EPDM) was carried out under different reaction conditions. A series of graft products of EPDM-graft-methyl methacrylate and acrylonitrile (EPDM-g-MAN), characterized by Fourier-transform infrared spectroscopy, was blended separately with styrene–acrylonitrile (SAN) resin to investigate their toughening effect on SAN matrix. The relationship between the polarity of EPDM-g-MAN and toughness of EPDM-g-MAN/SAN resin blends (AEMS) was evaluated. The compatibility and morphologies of AEMS were probed by dynamic mechanical analysis, transmission electron microscopy, and scanning electron microscopy to determine the toughing mechanism of the blends. Thermogravimetry results showed that the thermal stability of AEMS was enhanced with the incorporation of EPDM-g-MAN graft copolymer.     

Reversible addition-fragmentation chain transfer polymerization of vinyl acetate and vinyl pivalate in supercritical carbon dioxide

Two highly supercritical CO₂-soluble, poly(vinyl acetate) (PVAc)-based macro-reversible addition-fragmentation chain transfer (RAFT) agents were synthesized. The RAFT agents were used for the first time in RAFT/macromolecular design via the interchange of xanthates (MADIX) and polymerization of vinyl acetate (VAc) and vinyl pivalate (VPi) in supercritical carbon dioxide (scCO₂). A homopolymer PVAc and a block copolymer PVAc-b-PVPi made by RAFT/MADIX polymerization were characterized, and the effects of time and RAFT agents on polymerization were examined. For the 8.4 wt% RAFT agent in VAc, the molecular mass (M _n ) of homopolymer PVAc was 26,000 g mol^?1 and PDI was 1.35. For the copolymerization of VPi using 9.8 wt% PVAc-RAFT agent in VPi for 24 h, the M _n and PDI of PVAc-b-PVPi reached 32,400 g mol^?1 and 1.42, respectively. These results suggest that the polydispersity can be controlled during the clean production of PVAc and PVPi by RAFT/MADIX polymerization in scCO₂.     

Rheological behavior of a LDPE/PS/SBS blending melt

The dynamic rheological behaviors are measured by small amplitude oscillatory shear on a rotational rheometer for a low-density polyethylene (LDPE)/polystyrene (PS)/styrene–butadiene–styrene (SBS) block copolymer blend with the tool of cole–cole plot. The morphology of the blend is measured by scanning electron microscope (SEM) micrograph, the storage moduli–angular frequency (G′–ω) data are fit by the Palierne model, and the relaxation time spectrum is investigated. The storage modulus and loss modulus of the LDPE/PS/SBS blend at low frequency increase when the weight ratio LDPE/PS increases from 10/90, reaches a maximum of 30/70, and drops thereafter. The cole–cole plots of some blends (10/90/3, 70/30/3, 90/10/3 and 100/0/3) have only one main arc due to compatibilizing effect of the SBS, and those of other blends (0/100/3, 30/70/3 and 50/50/3) have a second arc or a long tail besides the main arc probably due to phase separation. The SEM micrographs of the LDPE/PS/SBS = 10/90/3, 30/70/3, 50/50/3 show sea-island, semi-co-continuous and co-continuous structure, respectively. G′–ω curve of two LDPE/PS/SBS = 30/70/3 and 50/50/3 blends shows a power law, and the power index is much lower than one (0.748 and 0.817), respectively, showing a co-continuous morphology also verified by the SEM micrographs. The experimental data of G′–ω curve of the LDPE/PS/SBS blends are fit by Palierne model, the deviation between the fit line and the experimental data increases gradually as the LDPE/PS weight ratio decreases from 90/10 to 10/90. For the LDPE/PS/SBS blends, the weighted relaxation spectra τH (τ)–τ show a main as well as a second arc or tail; the former corresponding to the relaxation of PS phase and the latter corresponding to that of LDPE phase. Due to the compatibilizing effect of SBS the relaxation time and spectrum strength of LDPE/PS = 50/50 (wt) blends are both increased.     

Composition and pH dependence on aggregation of SiO2–PVA suspension for the synthesis of porous SiO2–PVA nanocomposite

Porous monolithic SiO₂–poly(vinyl alcohol) (PVA) nanocomposites were fabricated by drying an SiO₂–PVA suspension. Depending on the amount of added PVA and pH value of the suspension, the Brunauer–Emmett–Teller surface areas, total pore volumes, and mean pore radii of the (100 ? x)SiO₂–xPVA (x = 0, 10, 20, 30 wt%) nanocomposites were 102–313 m² g^?1, 0.61–1.42 cm³ g^?1, and 8.1–14.7 nm, respectively. Some cracks were observed in the monolithic SiO₂–PVA nanocomposite, affected by the pore size. To elucidate crack generation, the correlation between the dispersion/aggregation in the SiO₂–PVA suspension and the pore size distribution of the nanocomposite was evaluated in terms of the added PVA amount and pH value. At x = 20 and pH 3, the SiO₂ particles and PVA aggregated in the suspension. The preparation of crack-free monolithic SiO₂–PVA nanocomposites was possible using the aggregated suspension owing to the low capillary force during drying because of the relatively large pores.     

Effects of in situ and ex situ formations of silica nanoparticles on polyethersulfone membranes

This study deals with the observed changes in the structure and performance of polyethersulfone (PES) membranes due to in situ formation and ex situ addition of silica particles (SiO₂). Hydrolysis and condensation of tetraethyl orthosilicate (TEOS) inside the PES polymer matrix and the reaction of TEOS with ammonium hydroxide were chosen to form in situ and ex situ SiO₂ formations, respectively. The resultant structure confirmed by X-ray diffraction for the composite PES membranes showed the retention of the amorphous nature even after the addition of SiO₂. The FTIR study revealed the functional groups corresponding to silica networks with enhanced OH signatures on the surface of the composite membranes. Field emission scanning electron microscopic images showed the variation in the surface and cross-sectional structures for the pure and composite membranes. Considerable reduction in the thickness of the skin, difference in the pore structure and ‘finger-like’ cross-sectional morphology with the presence of SiO₂ was observed in PES membranes. Both SiO₂/PES composite membranes were showed a minor change in their glass transition temperature (T _g). The ex situ methodically formed composite membrane displayed an increase in the pure water flux and decrease in bovine serum albumin rejection as compared to in situ and pure PES membranes. These kinds of composite membranes can be utilized for water treatment applications demanding higher water flux.     

Preparation of l-Lactide/3-Glycidyloxypropyltrimethoxysilane Copolymeric Materials with Various Catalysts

Copolymerization reactions of 3-glycidyloxypropyltrimethoxysilane (GPTS) with l-lactide (LLA) at 100 °C for different time intervals are performed by various catalysts such as zirconium perfluoroheptanoate, and commercially available Tin(II) chloride (SnCl₂) and sodium trimethylsilanolate (NaOSiMe₃). Homo- and copolymers are characterized by FTIR, ¹H- and ¹³C-NMR spectroscopies, electrospray ionization mass spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and gel permeation chromatography. All selected catalysts are effective in ROP of monomers. Especially, SnCl₂ is more reactive catalyst in the copolymerization of LLA/GPTS. The structure of final product is found as random copolymers.     

Effect of nafion membrane thickness on performance of vanadium redox flow battery

The performance of vanadium redox ow batteries (VRFBs) using different membrane thicknesses was evaluated and compared. The associated experiments were conducted with Nafion® 117 and 212 membranes that have 175 and 50 μm of thickness, respectively. The charge efficiency (CE) and energy efficiency (EE) of VRFB using Nafion® 117 were higher than those of VRFB using Nafion® 212, while power efficiency was vice versa. In terms of amounts of charge and discharge that are measured in different charging current densities, the amounts in VRFB using Nafion® 212 are more than that in VRFB using Nafion® 117. To further characterize the effect of membrane thickness on VRFB performance, electrochemical impedance spectroscopy (EIS) and UV-vis. spectrophotometer (UV-vis) were used. In EIS measurements, VRFB using Nafion® 117 was more stable than that using Nafion® 212, while in UV-vis measurements, vanadium crossover rate of VRFB usingNafion® 212 (0.0125M/hr) was higher than that of VRFB using Nafion® 117 (0.0054 M/hr). These results are attributed to high crossover rate of vanadium ion in VRFB using Nafion® 212. With these results, vanadium crossover plays more dominant role than electrochemical reaction resistance in deciding performance of VRFB in condition of different membranes.     

Receptors of sex pheromones and abstinons inMusca domestica andGlossina morsitans

Receptors arranged in two pairs on the inner and outer sides of the proximal end of the tibia of legs ofMusca domestica L. andGlossina morsitans morsitans Westwood are described here for the first time. In the male fly, these receptors function in perception of sex pheromones, as demonstrated in experiments in which the sense organs were coated with paraffin. Similar techniques showed that sense organs for abstinon are located on the tarsi. Scanning electron microscopy and light microscopy show that the tibial sense organs ofMusca may be sensilla of the coeloconic type.     

Selected factors influencing neurohormonal regulation of sex pheromone production inHeliothis species

Sex pheromone production and release in females ofHeliothis species exhibit a diel periodicity. Phermone production is controlled by a hormone, the pheromone biosynthesis activating neuropeptide (PBAN). Release of PBAN to activate pheromone production follows a circadian rhythm. InH. zea females, mating terminates pheromone production. An unidentified hemolymph-borne factor is transferred from the male to the female during mating. It is speculated that this factor interacts with the release mechanism of PBAN to prevent further production of the pheromone following mating. Wild females ofH. phloxiphaga (reared from larvae collected in the field) did not produce or release the sex pheromone unless kept in association with the host plant. Pheromone production could be induced in these females by the injection of PBAN. It is suggested that a signal from the host plant is essential to trigger the release of PBAN to induce pheromone production.     

Quantitation of a bioactive metabolite in undisturbed rhizosphere—Benzyl isothiocyanate fromCarica papaya L.

A “continuous root exudate trapping system” was recently developed in this laboratory by which the allelopathic metabolites from the undisturbed rhizosphere ofHemarthria altissima (Poir.) Stapf. et Hubb. were collected. Twelve phenolic compounds were identified by capillary GC-MS (Tang and Young, 1982). In this report, we further describe its use for the quantitation of benzyl isothiocyanate (BITC), a highly bioactive volatile compound, in the rhizosphere of growing papaya plants. Samples were collected from 64 individual papaya (Carica papaya L.) trees of Waimanalo and Higgins cultivars. Hydrophobie compounds collected on XAD-4 columns were eluted with acetone and the levels of BITC were determined by a gas Chromatograph equipped with a sulfur-specific flame photometric detector. For 2-month-old trees, the rate of BITC released from the root system of Waimanalo was 2.03 ± 0.85μg/tree/day. From Higgins, it was 2.36 ± 1.06 μg/tree/day. It has been reported that Waimanalo is resistant whereas Higgins is susceptible toPhytophthora palmivora Butl., the major root rot fungal pathogen of papaya trees in Hawaii. Our results lead us to conclude that the rate of BITC released alone cannot account for differences in the resistance of these two cultivars to the pathogen.     

Rapid analysis of dimer acid by HPLC/FID

A method was developed for the rapid analysis of polymerized fatty acids (dimer acid) using normal phase HPLC with a flame ionization detector (FID). The use of analytical scale HPLC with the FID is a significant limprovement over existing methodology for dimer analysis. The HPLC analysis takes only 25 min per sample, with no derivatization required. The FID response is linear for dimer samples from 10% to 90% monomer content. Absolute measurement precision is typically less than 0.5 area percent. Recovery of synthetic dimer blends averaged 102%. Results for the analysis of commercial dimer acid are comparable to those obtained using an HPLC/gravimetric method. The HPLC/FID method is applicable to the analysis of crude dimer as well as the finished dimer product.     

Preparation and characterization of a new polymer/pharmaceutical-based composite. Part I: Meloxicam

Composites of low-density polyethylene (LDPE), poly(ethylene-co-vinyl acetate) (EVA), poly(ethylene-co-octadecene), and an LDPE/EVA blend were prepared with different amounts of meloxicam (1, 3 and 5 wt %) by the melt blending process. Meloxicam was homogenously dispersed in polymer matrices. The polymer–meloxicam composites showed thermal behavior and thermal characteristics similar to those of the original polymers. Meloxicam release from the composites was examined in vitro for 50 days. The composites were incubated in phosphate-buffered solution and meloxicam concentration was determined by high-performance liquid chromatography. The prolonged release of the drug indicates that meloxicam-loaded plastic rings offer potential for control of reproduction and chronic inflammatory conditions.     

The effect of carbon black and HALS hybrid systems on the UV stability of high-density polyethylene (HDPE)

In the present study, attempts were made to study the effect of a hybrid UV stabilizing system on high-density polyethylene (HDPE). For this purpose, high molecular weight PE was used to prepare samples containing different amounts of hindered amine light stabilizer (HALS), carbon black (CB) and HALS/CB systems as UV stabilizers. All samples were exposed to UV irradiation simulating 4 and 8 years of exposure to solar irradiation in central part of Iran (Yazd). FTIR results were used to estimate the carbonyl index (CI) of the samples. It showed that CI increased as UV exposure time increased. However, it was found out that in the samples having both stabilizers (HALS/CB), CI value was much less compared to other samples indicating that the presence of hybrid system would show a synergism effect on UV stabilization of HDPE. The gel content of all samples was measured and it confirmed the same results. The PECH sample (containing HALS and CB) showed the least gel content after equivalent time of 4 and 8 years of exposure (2 and 3.5 wt%, respectively) which was in accordance with CI result. Furthermore, the effect of different UV stabilizing systems on the mechanical properties of HDPE was studied. For this purpose, elastic modulus, elongation-at-break and yield stress of the samples were measured. It was found out that HALS/CB hybrid system preserved the mechanical properties of HDPE much better than the other systems, which was attributed to the synergistic effect of the simultaneous use of HALS and CB.     

Study on compatibility of recycled polypropylene/high-density polyethylene blends using rheology

The compatibilization of recycled polypropylene (PP) and high-density polyethylene (HDPE) was studied using two types of compatibilizers: 5 wt% PP-grafted-maleic anhydride (5 wt% MAPP) and 5 wt% HDPE-grafted-maleic anhydride (5 wt% MAHDPE), using a cone and plate rheometer. Maleic anhydride (MAH) was grafted onto PP or HDPE via peroxide initiated melt grafting technique. Blends containing highest amount of pure HDPE exhibited maximum values for tensile strength, complex viscosity, dynamic and loss modulus compared to similar blends developed using recycled HDPE. The latter properties of all the compatibilized blends were higher compared to that of uncompatibilized blends. Studies on rheology of the pure and recycled polymer and its compatibilized blends have thrown some light on the molecular weight distribution of these materials. High shear yielding characteristics were noted for MAHDPE compatibilized blends containing high percentage of HDPE. Scanning electron microscopy showed that blends containing a high percentage of HDPE and HDPE based compatibilizer exhibit a dispersed morphology. Fourier transform infrared spectrometer characterization was conducted to check if compatibilization occurred between recycled PP and HDPE.     

Gossypol analysis in cottonseed oil by HPLC

Gossypol in cottonseed oil was selectively separated by the extraction of cottonseed oil with a hexane and N,N dimethyl formamide:water (2∶1, v/v) solvent mixture. After filtration, the extract was injected into the HPLC with the elution time less than 15 min. The spectrophotometric method showed 2 to 5 times higher values of gossypol content in different types of glanded cottonseed oil than did the HPLC method. This is probably due to the gossypol derivatives and coloring interferences reacting with p-anisidine to develop color and increasing the absorbance reading, whereas gossypol was separated and detected in the HPLC method.     

Rheological Behavior of Polycarbosilane Part II: Effect of Heterometal (Al) Content and Nature of Bonding with Si of Polycarbosilane

A few aluminum containing polycarbosilanes named AlOR-PCS and Alac-PCS have been synthesized by the reaction of aluminum isopropoxide (AlOR) and aluminum acetylacetonate (Alac) with polycarbosilane (PCS), respectively. These materials were characterized by Fourier Transform Spectroscopy (FTIR), Thermo gravimetric Analysis (TGA) and Gel Permeation Chromatography (GPC). The rheological properties of these compounds were studied with respect to time, temperature and atmosphere (inert & air). It has been observed that the increase in metal content enhances the crosslinking of the PCS chains. Under similar conditions, the crosslinking of AlOR-PCS derivatives was found slower than Alac-PCS. GPC analysis of the samples showed the increase in molecular weight of these compounds compared to virgin PCS. TGA showed improved ceramic yield with increasing metal content. Alac-PCS gave higher ceramic yield than AlOR-PCS for similar molar ratios of metal complexes.     

A comparative study of different microchips for capillary electrophoresis with electrochemical detection

This work describes a comparison of the performance of different microchip configuration for microchip capillary electrophoresis with electrochemical detection. Two electrodes gold and multistrand carbon fibers and two microchip construction materials polydimethylsiloxane/polydimethylsiloxane (PDMS/PDMS) and polydimethylsiloxane/glass hybrid (PDMS/glass) were analyzed. The electrode is integrated into the microchip for in-channel triple pulse amperometric detection. Two different mixtures were analyzed (i.e., paracetamol (PA)-4-aminophenol (4-AP) and Dopamine (DO)-Dopac) to demonstrate the electrode and microchips performance. Other variables, such as injection and separation potentials, buffer pH, surfactants addition and injection time, were also analyzed. Hydrodynamic voltammograms were used to select working potential values, and +0.9 V for PA and 4-AP and +0.8 V for DO and dopac were chosen. The migration potential was modified in the 1,500–2,500 V range, and the employed value depends on the microchip materials. The separation process was tested by analyzing the current and migration time variation coefficients. The experimental results demonstrated that the hybrid PDMS/glass microchip with a carbon fiber electrode exhibited a better performance for both samples analyzed.     

Abstinons

Glossina morsitans morsitans Westwood andMusca domestica Linne have an efficient strategy for preventing wasteful homosexual activity in males: hexane-soluble substances on the cuticle of the male flies terminate courting by other males on contact. The inhibitory activity of these materials is demonstrated by the abstention of males from mating with females treated with male extract.     

CsHSO4 as proton conductor for high-temperature polymer electrolyte membrane fuel cells

The influence of CsHSO₄ inorganic solid acid was evaluated as a possible proton conductor in the catalyst layer of ABPBI (poly(2,5-benzimidazole))-based high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Gas diffusion electrodes (GDEs) were prepared with fixed polytetrafluoroethylene (PTFE) and polyvinylidene diflouride (PVDF) binder content, while the CsHSO₄ loading was varied. Porosimetry data showed that the addition of 10 % CsHSO₄ to the PVDF GDE increased the porosity across all the pore regions, whereas the addition of 10 % CsHSO₄ to the PTFE GDE decreased the GDEs porosity. The CsHSO₄ MEAs showed good proton transfer dynamics and low resistance for fuel cell operation. An optimum loading of 10 % CsHSO₄ in conjunction with either of the binders was observed, with CsHSO₄–PVDF GDE achieving peak power of 498.2 mW cm^?2 at a cell voltage of +352 mV. Higher CsHSO₄ loadings increased the charge transfer resistance and lowered the cell performance of these GDEs.