New Poly(aniline-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="Italic">o</Emphasis>-phenylenediamine)/Kaolinite Microcomposites for Water Decontamination

Copolymers of aniline and o-phenylenediamine/kaolinite composites were synthesized by 5:1 molar ratios of the respective monomers with different percentages of nanoclay via modified in situ chemical co-polymerization. The results were verified by measuring the FT-IR and UV–vis absorption spectra for PANI-o-PDA/kaolinite composites. The thermal behaviour of the copolymer and composites was studied. PANI-o-PDA/kaolinite composites were thermally more stable than pure copolymer. Surface morphology of copolymer composites was recorded at different magnification power by SEM which revealed whitish micrometric beads distributed all over the field with particle size in the range of 0.122–0.233 μm. This work demonstrates that the PANI-o-PDA/kaolinite composites particles can be considered as potential adsorbents for hazardous and toxic metal ions of water from lake El-Manzala, Egypt. All of Cd(II), Cu(II), and Pb(II) posed dangerous health risk to the local population via fish consumption.     

In Vivo and In Vitro Degradation Studies for Poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyhexanoate) Biopolymer

Studies have shown that the copolymer poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB-co-HHx)] possesses favorable mechanical properties for use in medical supplies and products (e.g., sutures, scaffolds, bone plates). One of the major under-addressed issues associated with the use of biodegradable, bio-based PHA polymers in resorbable medical products is the correlation between the mechanical properties and the in vivo material degradation over time. In this study, P(HB-co-17 mol% HHx) matrices were mechanically tested after either incubation in cultures of human embryonic kidney cells (HEK) for in vitro degradation studies for up to 4 weeks, or inserted into Danio rerio (zebrafish) tissues for in vivo degradation studies for up to 7 weeks. The mechanical properties and scanning electron microscopy (SEM) images of the degraded materials were examined and later correlated to understand the degradation phenomenon. Our results show that Young’s modulus of P(HB-co-17 mol%HHx) during in vitro studies decreased from 3.26 to 2.42 GPa within 4 weeks, and in vivo breakdown resulted in a significant decrease in Young’s modulus with a decrease from 3.26 to 0.51 GPa and a mass loss of 59 % within 7 weeks. SEM images showed the development of pores and cracks on the surface of the material over time. Plasticization and recrystallization were observed and likely play a role in the alteration of mechanical properties.     

Estimation on Biodegradability of Poly (3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyvalerate) (PHB/V) and Numbers of Aerobic PHB/V Degrading Microorganisms in Different Natural Environments

To assess the capacity of the natural environment for degrading PHB/V, the film-MPN method proposed previously was modified to estimate the numbers of PHB/V degrading microorganisms (degraders) in various environments. The First-Order Reaction (FOR) model was used to determine the appropriate incubation period for the method. Numbers of aerobic PHB/V degraders were estimated in garden soil, paddy field soil, farm soil, river bank soil, infertile garden soil, river water, activated sludge, and seawater by the film-MPN method. Results were compared with those estimated by the clear-zone technique and showed that the film-MPN method was suitable for estimating the numbers of PHB/V degraders in the environments tested. On the other hand, biodegradability of injection molded PHB/V samples was investigated in several kinds of environments. The changes of weight were studied and results showed that biodegradability of PHB/V related to the numbers of PHB/V degraders in similar ecosystem in different regions. In different environments the biodegradability of PHB/V not only related to the number of PHB/V degraders, but also depended on whether there were conditions for the PHB/V degraders to grow and proliferate easily in the environment.     

Adsorption of Crystal Violet Dye from Aqueous Solution by Poly(Acrylamide-<Emphasis Type="Italic">co</Emphasis>-Maleic Acid)/Montmorillonite Nanocomposite

Poly(acrylamide-co-maleic acid)/montmorillonite nanocomposites, were synthesized via in situ polymerization with different maleic acid and MMT content. The capability of the hydrogel for adsorption of crystal violet (CV) was investigated in aqueous solutions at different pH values and temperatures. The pseudo-second-order kinetics model could fit successfully the adsorption kinetic data. The effects of maleic acid to acrylamide molar ratio (MA_R), weight percent of MMT (MMT%), the pH of medium and the solution temperature (T) on the CV adsorption capacity (q _e ) of adsorbents were studied by Taguchi experimental design approach. The results indicated that increasing the MMT% leads to a greater q _e . The q _e value of adsorbents increased also with increasing both MA_R and pH, while reduced when the temperature of medium increased. The relatively optimum conditions to achieve a maximum CV adsorption capacity for P(AAm/MA)/MMT adsorbents were found as: 0.06 for MA_R and 5 % of MMT%, medium pH = 7 and T = 20 °C.     

Synthesis and Properties of <Emphasis Type="Italic">N</Emphasis>-Maleyl Chitosan-Cross-Linked Poly(Acrylic Acid-co-Acrylamide) Superabsorbents

A high-swelling superabsorbent was synthesized with biodegradable N-maleyl chitosan as cross-linker, acrylic acid (AA) and acrylamide (AM) as the monomers, ammonium peroxodisulfate–sodium bisulfite (NaHSO₃) as redox initiation system, by means of aqueous solution polymerization. The best reaction condition was based on the orthogonal experiment design. The optimal conditions on distilled water absorbency and on 0.9 wt% NaCl solution absorbency were monomer concentration 20 wt%, mole ratio of AA to (AA + AM) 60%, the neutralization degree of AA 40%, cross-linker concentration 2% and monomer concentration 25 wt%, mole ratio of AA to (AA + AM) 60%, neutralization degree of AA 50% and cross-linker concentration 1%, respectively. Factors influencing the water absorbency of superabsorbent also were investigated, by single factor experiment method. The absorbency of superabsorbents in distilled water and 0.9 wt% NaCl solution increased and then decreased with the increasing of monomer concentration, mole ratio of AA to (AA + AM) and degree of neutralization of AA. With the increasing of cross-linker concentration, the absorbency in distilled water increased and then decreased, but it decreased all the time in 0.9 wt% NaCl solution. In enzymatic degradation tests, the weight loss of superabsorbent was related to the content of cross-linker.     

Purification and Properties of Extracellular Poly(3-hydroxybutyrate) Depolymerase Produced by <Emphasis Type="Italic">Aspergillus fumigatus</Emphasis> 202

An extracellular poly(3-hydroxybutyrate) (PHB) depolymerase produced by a thermotolerant fungal soil isolate, Aspergillus fumigatus 202, was purified and characterized. Maximum PHB depolymerase production was obtained at the end of 48 h with initial medium pH 7.0 and 45 °C in Bushnell Haas Minerals medium containing PHB as sole source of carbon. The PHB depolymerase was purified using size exclusion chromatography to a fold purification of 20.62 and 61.62% yield. SDS-PAGE and isoelectric focusing revealed the molecular weight and pI of the purified enzyme as 63,744 Da and 4.2, respectively. N-terminal amino acid sequence of purified enzyme was HAXDAYLVK. This non-glycosylated enzyme was most active at pH 9.0 and 45 °C. Purified enzyme was inactivated by N-bromosuccinimide and dithiothreitol suggesting the involvement of tryptophan residues and disulfide bonds at its active site. Nonionic detergents like Tween 20, Tween 80 and Triton X-100 inhibited the enzyme activity. Ions like Ca⁺² and Mg⁺² (5 mM) increased the enzyme activity 1.5 times. Fe⁺² effectively inhibited the enzyme activity to 88% whereas Hg⁺² completely inhibited the enzyme.     

Physical and Thermal Analysis of the Degradation of Poly(3-Hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-4-Hydroxybutyrate) Coated Paper in a Constructed Soil Medium

The degradation of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P(3HB-co-4HB)) coated brown Kraft paper and its components in a constructed soil environment was investigated. Soil burial tests were carried out over 8 weeks. Weight loss measurements, photographic analysis, environmental scanning electron microscopy (ESEM), dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) were conducted to assess the physical, structural, mechanical and thermal behavior before and after the soil burial test. Paper showed the highest physical degradation and weight loss. With respect to the control samples, the stiffness of the partially degraded samples decreased. The overall crystallinity of the biopolymer and the coated paper was affected significantly by burial. The pure biopolymer’s weight loss was substantially enhanced when coated on paper. This result reveals a possible increased microbial population in the coated paper relative to the pure biopolymer.     

Blending Modification of PHBV/PCL and its Biodegradation by <Emphasis Type="Italic">Pseudomonas mendocina</Emphasis>

Poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) is a biodegradable polymer synthesized in microorganisms. The application of PHBV is limited by certain material disadvantages. Poly(ε-caprolactone) (PCL) possesses excellent thermodynamic and mechanical properties and was used to modify PHBV in the presence of triethyl citrate (TEC) and dicumyl peroxide (DCP), which was used as plasticizer and grafting agent, respectively. The effects of PCL and additive agents on the mechanical, thermal, amphipathic and degradability behaviors of the blends were investigated. The results showed that the mechanical properties of the PHBV blends improved by PCL incorporation and improved even further after TEC and DCP addition. The addition of DCP could not induce an increase in crystallization temperature but improved the crystallization degree of the blends. The presence of hydrophilic groups in TEC leads to an apparent increases in the hydrophilicity of the PHBV blends. A PHBV/PCL blend (40/60) with TEC (20 wt.%) and DCP (0.5 wt.%) was chosen for its good mechanical properties and hydrophilicity. The chosen ratio of the blends was also shown a preferable degradation activity by biodegradation assay using Pseudomonas mendocina. The addition of TEC and DCP has no conspicuous negative effect on the biodegradation.     

A Microscopic Study of Paper Decayed by <Emphasis Type="Italic">Trichoderma harzianum</Emphasis> and <Emphasis Type="Italic">Paecilomyces variotii</Emphasis>

The current study is interested in evaluating the decay of cotton, Whatman and chemical pulp caused by Trichoderma harzianum and Paecilomyces variotii. The structural changes of the paper were evaluated by Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM). The SEM results show differences in hyphae colonization and paper decay patterns between studied species under the current study; P. variotii caused an eroded structure in the cotton (cavity forming), whereas the initial T. harzianum colonization produced rupture and erosion (soft-rot decay type II) for the three types of paper ,the gaps were elongated with sharp pointed ends, which consisted either of individual cavities or in chains. Moreover, FTIR results confirmed that there a relationship could be observed between fungal decay and crystalline cellulose content because the intensity of peaks at 1335 and 1111 cm^?1 significantly decreased due to the fungal decay. Furthermore, the intensity of O–H stretching absorption slightly decreased, and this may be attributed to hydrolysis of cellulose molecules.     

Biosynthesis of Poly(3-hydroxybutyrate) from Cheese Whey by <Emphasis Type="Italic">Bacillus megaterium</Emphasis> NCIM 5472

Microbial polyhydroxyalkonate such as homopolyester of poly(3-hydroxybutyrate) (PHB) was produced from cheese whey by Bacillus megaterium NCIM 5472. Due to their numerous potential industrial applications, the focus was given to competently enhance the amount of PHB produced. The amount of PHB produced from whole cheese whey, and ultrafiltered cheese whey was first compared, and after observing a rise in PHB production by using ultrafiltered cheese whey, cheese whey permeate was chosen for further analysis. The presence of PHB was then confirmed by GCMS. Since the main aim of the study was to increase the amount of PHB produced through batch fermentation, various process parameters like time, pH, C/N ratio, etc. were optimized. After optimization, it was found that B. megaterium NCIM 5472 was capable of accumulating 75.5% of PHB of its dry weight and a PHB yield of 8.29 g/L. The chemical structure of the polymer was further analyzed by using FTIR and NMR spectroscopy methods. Also, the physical and thermal properties were studied by using Differential scanning calorimetry and Thermogravimetric analysis. It was found that the polymer produced had excellent thermal stability, thus allowing the possibility to exploit its properties for industrial purposes such as adhesives, packaging materials, etc.     

Gene Cloning and Characterization of a Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactic Acid) Depolymerase from <Emphasis Type="Italic">Pseudomonas</Emphasis> sp. Strain DS04-T

A gene encoding a poly(l-lactic acid) (PLA) depolymerase from Pseudomonas sp. strain DS04-T was cloned and overexpressed in Escherichia coli. The recombinant PLA depolymerase with a molecular weight of 19.2 kDa was purified to homogeneity. The optimum pH and temperature of the PLA depolymerase are 8.5 and 60 °C, respectively. K⁺, Ca²⁺ and Ni²⁺ enhance the enzyme activity, while Na⁺, Zn²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Mn²⁺ and Co²⁺ inhibit it. The inhibition of different chemicals on the PLA depolymerase activity were examined, in which EDTA was found to have a significantly inhibitory effect. The main degradation product of the depolymerase is identified as lactic acid monomer by mass spectrometric analysis. Physicochemical properties, substrate specificity and sequence analysis indicated that PME is a new type of PLA depolymerase.     

Purification and biochemical characterization of recombinant alcohol dehydrogenase from the psychrophilic bacterium <Emphasis Type="Italic">Pseudomonas</Emphasis><Emphasis Type="Italic">frederiksbergensis</Emphasis>

A gram-negative psychrophilic bacterium, with potential for biodegradation of long-chain n-alkanes was isolated from ice samples collected in Spitzbergen, Denmark. On the basis of results of biochemical and morphological tests and sequence analysis of 16S rRNA, the strain was identified as Pseudomonas frederiksbergensis. In this work, a short-chain NAD⁺-dependent alcohol dehydrogenase (alcDH) (Accession number: AAR13804) from the P. frederiksbergensis was cloned and transformed in E. coli BL21 (3DE) competent cells. The alcDH activity was highest in the crude extract of cells induced with 1.0 mM IPTG. The recombinant alcDH enzyme was purified to 93.4% homogeneity using three consecutive purification steps including ammonium sulphate, Q-Sepharose Fast Flow column and gel filtration chromatography employing Superdex 200 10/30 HR column. Enzyme enrichment and yield levels of 31.4 folds and 25.5%, respectively, were achieved. While the subunit molecular mass of the enzyme was determined on SDS-PAGE to be ~38 kDa, the aggregated native form of the enzyme had a molecular mass of ~238 kDa by gel filtration analysis. Reaction conditions optima for the recombinant alcDH were determined with propan-1-ol as the substrate. While the optimum pH was 9, the optimum temperature was 35 °C. The alcDH enzyme exhibited moderate thermal stability with half-lives of 150 min at 55 °C, 27 min at 65 °C and 8 min at 75 °C. Results for kinetic parameters indicated that the apparent K _m value for alcDH with propan-1-ol as the substrate was found to be 1.42 mM and the V _max value was 0.63 mmol mg⁻¹ min⁻¹. Experimental evidence revealed that the recombinant alcDH exhibited a wide range of substrate specificity, with higher levels of specific activity for aliphatic alcohols as compared to secondary alcohols. Taken together, the present study highlights the potential of alcDH as a member of cold-adapted enzymes in several key biotechnological applications including environmental bioremediation and biotransformations. It is envisaged that, with the ongoing screening of microorganisms and metagenomes, directed evolution approaches and the subsequent overexpression of recombinant proteins, more enzymes will be found that are suitable for bioremediation purposes.     

The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Biodegradation of Poly(vinyl alcohol) and Bacterial Cellulose Composites by <Emphasis Type="Italic">Aspergillus niger</Emphasis>

The ability of fungal strains to attack a composite material obtained from poly(vinyl alcohol) (PVA) and bacterial cellulose (BC) is investigated. The fungal strain tested was Aspergillus niger. This fungal strain was able to change not only the polymer surface from smoother to rougher, but also to disrupt the polymer. The degradation results were confirmed by visual observations, scanning electron microscopy (SEM) analyses, X-ray diffraction analyses and FTIR spectra of the film samples. SEM micrographs confirmed the growth of fungi on the composite film surface. The degree of microbial degradation depends on culture medium and on composition of polymeric materials, especially on PVA content. The biodegradation process is accelerated by the presence of glucose in the culture medium as an easily available carbon source.     

Biodegradable Compatibilized Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Thermoplastic Polyurethane Blends: Design,Preparation and Property Testing

Biodegradable blends of poly(l-lactide) (PLL) toughened with a polycaprolactone-based thermoplastic polyurethane (TPU) elastomer and compatibilized with a purpose-designed poly(l-lactide-co-caprolactone) (PLLCL) copolymer were prepared. Both 2-component (PLL/TPU) and 3-component (PLL/TPU/PLLCL) blends of various compositions were prepared by melt mixing, hot-pressed into thin films and their properties tested. The results showed that, although the TPU could toughen the PLL, the blends were immiscible leading to phase separation with the TPU domains distributed in the PLL matrix. However, addition of the PLLCL copolymer could partially compatibilize the blend by improving the interfacial adhesion between the two phases. Biodegradability testing showed that the blends were biodegradable and that the PLLCL copolymer could increase the rate of biodegradation under controlled composting conditions. The 3-component blend of composition PLL/TPU/PLLCL?=?90/10/10 parts by weight was found to exhibit the best all-round properties.     

Molecular Structure and Crystallization Dynamics of Poly(3-hydroxyl alkanoate) with Medium-Chain Length Biosynthesized from <Emphasis Type="Italic">Pseudomonas putida</Emphasis>

The molecular structure of poly(3-hydroxyalkanoate) (P3HA) with medium-chain length, biosynthesized from Psuedomonas putida (P. putida), was investigated by thermal analysis, X-ray diffraction, and infrared spectrum. Cultivation in a medium of nonanoic acid and a mixed substrate of nonanoic acid and glycerin as carbon sources provided P3HA with monomer units of 7 and 9 carbons (P3HA_n) and 5, 6, 7, 8, 9, and 10 carbons (P3HA_mix). Since these P3HA has comparatively long side chains, the crystallinity was as low as about 10%. It was suggested that the hydrogen bonding plays an important role in constructing the crystal. The lamellar thickness was 1.20 nm, estimated from the melting temperature depression. This lamellar thickness corresponds to two repeating units. Crystallinity depending on time was observed by the CO stretching mode in the infrared spectrum, and then Avrami’s theory was applied to analyze the crystallization mechanism. The crystallization rate of P3HA_n was very low, on the order of a few hours. An Avrami exponent of 1.45 was estimated from the slope of the Avrami plot. This shows that the conformational arrangement is presumably promoted along the chain axis. The slow crystallization is attributed to the long side chain, which prevents aggregation of the polymer chains.     

Mechanical Properties of Layered Laminated Woven Bamboo <Emphasis Type="Italic">Gigantochloa Scortechinii</Emphasis>/Epoxy Composites

This study investigated the application of bamboo as a natural composite, in which its potential as a composite material had been examined for 2–6 layers. In precise, the woven bamboo (BW) formed the culm fiber composite with an average of 0.5 mm thickness and 5.0 mm width strip. In addition, this study looked into a specific type of bamboo species known as Gigantochloa Scortechinii (Buluh Semantan), which can be found in Malaysia. This laminated plain BW, which had been reinforced with epoxy (EP), was developed by applying the hand lay-up technique. After that, the specimens were characterized via mechanical analyses, for instance, tensile, flexural, hardness, and impact tests. As a result, the 2-layer BW had displayed rather excellent results chiefly due to the incorporation of epoxy composite, although this is exceptional hardness value.     

Catalytic co-pyrolysis of <Emphasis Type="Italic">Pterospermum acerifolium</Emphasis> and plastic waste

The continuous increase in generation of solid wastes and gradual declining of fossil fuels necessities the development of sustainable conversion technologies. Recent studies have shown that the addition of biomass with hydrogen-rich co-reactants (plastics) altogether enhances the quality of bio-fuels using pyrolysis process. It was observed that red mud (which is produced as by-product in Bayer process) was used as a catalyst in few conversion process. In this study, pyrolysis of biomass (Pterospermum acerifolium) and waste plastic mixture with activated red-mud catalyst was investigated using thermo-gravimetric analysis. The kinetic parameters (activation energy and pre-exponential factor) of this process were determined using distributed activation energy model (DAEM). The DAEM was effectively applied to decide the activation energy (E) and pre-exponential factor (A) for each sample at various conversions during the catalytic co-pyrolysis. The biomass, plastic, biomass–plastic, and biomass–plastic–catalyst exhibited activation energies in the ranges of 78–268, 172–218, 67–307, and 202–292 kJ/mol, respectively.     

<Emphasis Type="Italic">Mesua ferrea</Emphasis> L. Seed Oil Based Highly Branched Environment Friendly Polyester Resin/Clay Nanocomposites

To develop a high performance environment friendly material, highly branched polyester/clay nanocomposites have been prepared from Mesua ferrea Linn seed oil-based polyester resin and hydrophilic bentonite nanoclay. The prepared nanocomposites were characterized by Fourier transform infra-red spectroscopy, X-ray diffractometer, scanning electron microscope, transmission electron microscope and rheological studies. Partial exfoliation of clay layers by the polymer chains with good interfacial interactions was observed in the nanocomposites. The formation of delaminated nanocomposites was manifested through the enhancement of tensile strength, scratch hardness, chemical resistance, impact resistance, thermostability, etc. The results show enhancement of three times in tensile strength and 18 °C in thermostability by inclusion of 5 wt% nanoclay as compared to the pristine polymer. By the influence of 5 wt% nanoclay four times enhancement in elongation at break as compared to the pristine polymer was noticed. Thus these nanocomposites have the potential to be used in many advanced applications.