Preparation and characterization of glycerol plasticized-pea starch/ZnO–carboxymethylcellulose sodium nanocomposites

Among natural polymers, starch is one of the most promising biodegradable materials because it is a renewable bioresource that is universally available and of low cost. However, the properties of starch-based materials are not satisfactory. One approach is the use of nano-filler as reinforcement for starch-based materials. In this paper, a nanocomposite is prepared using ZnO nanoparticles stabilized by carboxymethylcellulose sodium (CMC) as the filler in glycerol plasticized-pea starch (GPS) matrix by the casting process. According to the characterization of ZnO–CMC particles with Fourier transform infrared (FTIR), Ultraviolet–visible (UV–vis), X-ray diffraction (XRD), transmission electron microscope (TEM) and thermogravimetric analysis (TG), ZnO (about 60 wt%) is encapsulated with CMC (about 40 wt%) in ZnO–CMC particles with the size of about 30–40 nm. A low loading of ZnO–CMC particles can obviously improve the pasting viscosity, storage modulus, the glass transition temperature and UV absorbance of GPS/ZnO–CMC nanocomposites. When the ZnO–CMC contents vary from 0 to 5 wt%, the tensile yield strength increase from 3.94 MPa to 9.81 MPa, while the elongation at break reduce from 42.2% to 25.8%. The water vapor permeability decrease from 4.76 × 10⁻¹⁰ to 1.65 × 10⁻¹⁰ g m⁻¹ s⁻¹ Pa⁻¹.     

Fabrication and characterization of poly(lactic acid)/acetyl tributyl citrate/carbon black as conductive polymer composites

By using acetyl tributyl citrate (ATBC) as the plasticizer of poly(lactic acid) (PLA) and carbon black (CB) as conductive filler, electrically conductive polymer composites (CPC) with different CB and ATBC contents were prepared. FTIR revealed that the interaction existed between PLA/ATBC matrix and CB filler and ATBC could improve this interaction. The rheology showed that ATBC could obviously decrease the shear viscosity and improve the fluidity of the composites but just the reverse for CB. With the increasing of CB contents, the enforcement effect, storage modulus, and glass-transition temperature increased but the elongation at break decreased. PLA/ATBC/CB composites exhibited the low electrical percolation thresholds of 0.516, 1.20, 2.46, and 2.74 vol % CB at 30, 20, 10, and 0 wt % ATBC. The conductivity of the composite containing 3.98 vol % CB and 30 wt % ATBC reached 1.60 S/cm. Scanning electron microscopy revealed that the addition of ATBC facilitated the dispersion of the CB in the PLA matrix. Water vapor permeability (WVP) showed that, at the same CB contents, the more ATBC contents there were, the less the values of WVP were.     

Preparation and properties of glycerol plasticized-pea starch/zinc oxide-starch bionanocomposites

A bionanocomposite was cast using ZnO nanoparticles stabilized by soluble starch (nano-ZnO) as filler in a glycerol plasticized-pea starch (GPS) matrix. According to the characterization of nano-ZnO particles by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TG) and transmission electron microscopy (TEM), ZnO nanoparitlces (70 wt%) were encapsulated by starch (30 wt%) in nano-ZnO particles of about 10 nm. In GPS/nano-ZnO nanocomposites, loading a low level of nano-ZnO particles improved the pasting viscosity, storage modulus, glass transition temperature and UV absorbance. When the nano-ZnO content varied from 0 to 4 wt%, the tensile yield strength and Young’s modulus increased from 3.94 to 10.80 MPa and from 49.80 to 137.00 MPa, respectively. The water vapor permeability decreased from 4.76 × 10^?10 to 2.18 × 10^?10 g m^?1 s^?1 Pa^?1. The improvement in these properties may be attributed to the interaction between the nano-ZnO filler and GPS matrix.     

Characterization of edible emulsified films with low affinity to water based on kefiran and oleic acid

New edible composite films based on kefiran and oleic acid (OA) at the ratio of 15, 25, and 35% (w/w) were prepared using emulsification with the aim of improving their water vapour barrier and mechanical properties. Film-forming solutions were characterized in terms of rheological properties and particle-size distribution. The impact of the incorporation of OA into the film matrix was studied by investigating the physical, mechanical, and thermal properties of the films. The water vapour permeability (WVP) of the emulsified films was reduced by approximately 33% by adding OA. The mechanical properties of kefiran films were also affected by adding OA: tensile strength was diminished, and elongation increased considerably. Differential scanning calorimetry showed that the glass transition temperature (T_g) of the kefiran film was −16 °C and was not considerably affected by adding OA. Therefore, OA could be incorporated into these films for some food-technology applications that need a low affinity toward water.     

High performance edible nanocomposite films containing bacterial cellulose nanocrystals

Bacterial cellulose obtained from Gluconacetobacter xylinus in the form of long fibers were acid hydrolyzed under controlled conditions to obtain cellulose nanocrystals. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) confirmed the formation of rod like cellulose nanocrystals having an average diameter and length of 20 ± 5 nm and 290 ± 130 nm respectively. These nanocrystals were used to prepare gelatin nanocomposite films and characterized for elucidating its performance. The formation of percolated networks of cellulose nanocrystals within gelatin matrix resulted in improving the mechanical properties of nanocomposites. The moisture sorption and water vapor permeability (WVP) studies revealed that the addition of cellulose nanocrystals reduced the moisture affinity of gelatin, which is very favorable for edible packaging applications. Results of this study demonstrated the use of bacterial cellulose nanocrystals (BCNCs) in the fabrication of edible, biodegradable and high-performance nanocomposite films for food packaging applications at relatively low cost.     

Preparation and properties of carboxylated styrene-butadiene rubber/cellulose nanocrystals composites

A series of carboxylated styrene-butadiene rubber (XSBR)/cellulose nanocrystals (CNs) latex composites were successfully prepared. The vulcanization process, morphology, dynamic viscoelastic behavior, dynamic mechanical property, thermal and mechanical performance of the XSBR/CNs composites were investigated in detail. The results revealed that CNs were dispersed uniformly in the XSBR matrix and formed a strong filler–filler network. The dynamic mechanical analysis (DMA) showed that the glass transition temperature (T_g) of XSBR matrix was shifted from 48.45 to 50.64 °C with 3 phr CNs, but decreased from 50.64 to 46.28 °C when further increasing CNs content up to 15 phr. The composites exhibited a significant enhancement in tensile strength (from 16.9 to 24.1 MPa) and tear strength (from 43.5 to 65.2 MPa) with loading CNs from 0 to 15 phr. In addition, the thermo-gravimetric analysis (TGA) showed that the temperature at 5% weight loss of the XSBR/CNs composites decreased slightly with an increase of the CNs content.     

Properties of blend film based on cuttlefish (Sepia pharaonis) skin gelatin and mungbean protein isolate

Blend films based on cuttlefish (Sepia pharaonis) ventral skin gelatin (CG) and mungbean protein isolate (MPI) at different blend ratios (CG/MPI = 10:0, 8:2, 6:4, 4:6, 2:8 and 0:10, w/w) prepared at pH 11 using 50% glycerol (based on total protein) as plasticizer were characterized. CG films incorporated with MPI at increasing amounts had the decreases in tensile strength (TS) (p < 0.05). The increases in elongation at break (EAB) were observed when CG/MPI ratios of 6:4 or 4:6 were used (p < 0.05). Decreased water vapor permeability (WVP) was obtained for films having the increasing proportion of MPI (p < 0.05). CG/MPI blend films with higher MPI proportion had lower film solubility and L*-values (lightness) but higher b*-values (yellowness) and ΔE*-values (total color difference) (p < 0.05). Electrophoretic study revealed that disulfide bond was present in MPI and CG/MPI blend films. However, hydrogen bonds between CG and MPI in the film matrix were dominant, as elucidated from FTIR spectroscopic analysis. Moreover, thermal stability of CG/MPI blend film was improved as compared to that of films from respective single proteins. Differential scanning calorimetry result suggested solid-state morphology of CG/MPI (6:4) blend film that consisted of amorphous phase of partially miscible CG/MPI mixture and the coexisting two different order phases of individual CG and MPI domains. Thus, the incorporation of MPI into gelatin film could improve the properties of resulting blend film, which were governed by CG/MPI ratio.     

Adverse effect of cake collapse on the functional integrity of freeze-dried bull spermatozoa

Under optimal freeze-drying conditions, solutions exhibit a cake-like porous structure. However, if the solution temperature is higher than the glass transition temperature of the maximally freeze-concentrated phase (T_g′) during drying phase, the glassy matrix undergoes viscous flow, resulting in cake collapse. The purpose of the present study was to investigate the effect of cake collapse on the integrity of freeze-dried bull spermatozoa. In a preliminary experiment, factors affecting the T_g′ of conventional EGTA buffer (consisting of Tris–HCl, EGTA and NaCl) were investigated in order to establish the main experimental protocol because EGTA buffer T_g′ was too low (−45.0 °C) to suppress collapse. Modification of the EGTA buffer composition by complete removal of NaCl and addition of trehalose (mEGTA buffer) resulted in an increase of T_g′ up to −27.7 °C. In the main experiment, blastocyst yields after ooplasmic injection of freeze-dried sperm preserved in collapsed cakes (drying temperature: 0 or −15 °C) were significantly lower than those of sperm preserved in non-collapsed cake (drying temperature: −30 °C). In conclusion, freeze-dried cake collapse may be undesirable for maintaining sperm functions to support embryonic development, and can be inhibited by controlling both T_g′ of freeze-drying buffer and temperature during the drying phase.     

In-situ silica incorporated carboxymethyl tamarind: development and application of a novel hybrid nanocomposite

A novel hybrid nanocomposite has been prepared using in situ incorporation of nano-sized filler (silica) onto carboxymethyl tamarind kernel polysaccharide (CMT). Various characterizations were employed to confirm that silica nano particles have been incorporated onto the polymer matrix. Rheological characteristics reveal stronger CMT-Si interaction at 0.5 and 1 wt% level. Beyond 1 wt% Si concentration, the interaction is less and so there is little drop in shear viscosity. Flocculation efficiency increases with incorporation of nano filler, maximum efficacy being observed at 1 wt% silica concentration. All the nanocomposites exhibited better flocculation characteristics in comparison to pure CMT.     

Nanocrystalline cellulose (NCC) reinforced alginate based biodegradable nanocomposite film

Nanocrystalline cellulose (NCC) reinforced alginate-based nanocomposite film was prepared by solution casting. The NCC content in the matrix was varied from 1 to 8% ((w/w) % dry matrix). It was found that the nanocomposite reinforced with 5wt% NCC content exhibits the highest tensile strength which was increased by 37% compared to the control. Incorporation of NCC also significantly improved water vapor permeability (WVP) of the nanocomposite showing a 31% decrease due to 5wt% NCC loading. Molecular interactions between alginate and NCC were supported by Fourier Transform Infrared Spectroscopy. The X-ray diffraction studies also confirmed the appearance of crystalline peaks due to the presence of NCC inside the films. Thermal stability of alginate-based nanocomposite films was improved after incorporation of NCC.     

Production and characterization of homopolymer poly(3-hydroxyvalerate) (PHV) accumulated by wild type and recombinant Aeromonas hydrophila strain 4AK4

Aeromonas hydrophila 4AK4 normally produces copolyesters (PHBHHx) consisting of 3-hydroxybutyrate (C4) and 3-hydroxyhexanoate (C6). Wild type and recombinant A. hydrophila 4AK4 (pSXW02) expressing vgb and fadD genes encoding Vitreoscilla haemoglobin and Escherichia coli acyl-CoA synthase respectively, were found able to produce homopolyester poly(3-hydroxyvalerate) (PHV) (C5) on undecanoic acid as a single carbon source. The recombinant grew to 5.59 g/L cell dry weight (CDW) containing 47.74 wt% PHV in shake flasks when growth was conducted in LB medium and PHV production in undecanoic acid. The cells grew to 47.12 g/L CDW containing 60.08 wt% PHV in a 6 L fermentor study. Physical characterization of PHV produced by recombinant A. hydrophila 4AK4 (pSXW02) in fermentor showed a weight average molecular weight (M_w) of 230,000 Da, a polydispersity of 3.52, a melting temperature of 103 °C and a glass transition temperature of −15.8 °C. The degradation temperature at 5% weight loss of the PHV was around 258 °C.     

Polyaniline-carbon nanotube composite film for cholesterol biosensor

Nanocomposite film composed of polyaniline (PANI) and multiwalled carbon nanotubes (MWCNT), prepared electrophoretically onto indium tin oxide (ITO)-coated glass plate, was used for covalent immobilization of cholesterol oxidase (ChOx) via N-ethyl-N′-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (NHS) chemistry. Results of linear sweep voltammetric measurements reveal that ChOx/PANI-MWCNT/ITO bioelectrode can detect cholesterol in the range of 1.29 to 12.93 mM with high sensitivity of 6800 nA mM⁻¹ and a fast response time of 10 s. Photometric studies for ChOx/PANI-MWCNT/ITO bioelectrode indicate that it is thermally stable up to 45 °C and has a shelf life of approximately 12 weeks when stored at 4 °C. The results of these studies have implications for the application of this interesting matrix (PANI-MWCNT) toward the development of other biosensors.     

Fabrication and characterization of citric acid-modified starch nanoparticles/plasticized-starch composites

Starch nanoparticles (SN) were prepared by delivering ethanol as the precipitant into starch-paste solution dropwise. Citric acid (CA) modified SN (CASN) were fabricated with the dry preparation technique. According to the characterization of CASN with Fourier transform infrared, X-ray diffraction, rapid visco analyzer, and scanning electron microscopy (SEM), amorphous CASN could not be gelatinized in hot water because of the cross-linking, and most of CASN ranged in size from about 50 to 100 nm. The nanocomposites were also prepared using CASN as the filler in glycerol plasticized-pea starch (GPS) matrix by the casting process. SEM revealed that CASN was dispersed evenly in the GPS matrix. As shown in dynamic mechanical thermal analysis, the introduction of CASN could improve the storage modulus and the glass transition temperature of CASN/GPS composites. The tensile yield strength and Young's modulus increased from 3.94 to 8.12 MPa and from 49.8 to 125.1 MPa, respectively, when the CASN contents varied from 0 to 4 wt %. Moreover, the values of water vapor permeability decreased from 4.76 x 10(-10) to 2.72 x 10(-10) g m(-1) s(-1) Pa(-1). The improvement of these properties could be attributed to the good interaction between CASN filler and GPS matrix. The comprehensive application of green chemistry principles were demonstrated in the preparation of CASN and CASN/GPS composites.     

Properties of biodegradable citric acid-modified granular starch/thermoplastic pea starch composites

Pea starch-based composites reinforced with citric acid-modified pea starch (CAPS) and citric acid-modified rice starch (CARS), respectively, were prepared by screw extrusion. The effects of granular CAPS and CARS on the morphology, thermal stability, dynamic mechanical thermal analysis, the relationship between the mechanical properties and water content, as well as the water vapor permeability of the composite films were investigated. Scanning electron microscope and X-ray diffraction reveal that the reinforcing agents, the granules of CAPS and CARS, are not disrupted in the thermoplastic process, while the pea starch in the matrix is turned into a continuous TPS phase. Granular CAPS and CARS can improve the storage modulus, the glass transition temperature, the tensile strength and the water vapor barrier, but decrease thermal stability. CARS/TPS composites exhibit a better storage modulus, tensile strength, elongation at break and water vapor barrier than CAPS/TPS composites because of the smaller size of the CARS granules.     

Deposition and characterization of ZnO thin films from a novel hexanuclear zinc precursor

The high nuclearity zinc complex, Zn₆(OAc)₈(μ-OH)₂(dmae)₂(dmaeH)₂ (1) (OAc = acetate and dmaeH = N,N′-dimethylaminoethanol), having a low decomposition temperature and sufficiently high solubility in non-polar solvents, was synthesized by a simple chemical technique in high yield and analyzed by melting point, elemental analysis, FTIR, NMR, single crystal X-ray crystallography and thermal analysis. Aerosol-assisted chemical vapor deposition technique was used to deposit a high-quality thin film with good adhesion to the glass substrate at relatively low temperature (320 °C). Scanning electron microscopy of the film shows clearly distinct crystallites of uniform shape with 2.4-2.9 μm size. Powder X-ray diffraction measurements have indicated the deposition of a crystalline phase of hexagonal ZnO with space group P63mc.     

Effect of lignocellulosic filler type and content on the behavior of polycaprolactone based eco-composites for packaging applications

This study was based on the influence of lignocellulosic fillers and content on the morphology, crystallization behavior and thermal, mechanical and barrier properties of fully biodegradable eco-composites based on polycaprolactone for packaging applications. The biodegradation in soil as a function of time was also analyzed. Composites with 5 and 15 wt% of cotton (CO); cellulose (CE) and hydrolyzed-cellulose (HCE) were prepared by melt-mixing. It was determined that, whereas lower content of CO and CE produced a decrease on the crystallinity of the matrix, HCE did not affect it. Increasing the filler content, the crystallinity degree of the matrix decreased at less extent, which was independent on the filler type. A clear reduction on the theoretical melting point, attributed to heterogeneous nucleation sites, took place for the lower content of CO and CE. Induction and half-crystallization times diminished when fillers were incorporated but the effect was less notorious at higher filler contents. All fillers enhanced the Young's modulus of the matrix but the optimal mechanical properties were not obtained with HCE, as was expected, but with CE. After analyzing the main parameters that affect the mechanical properties of the composite; such as morphology, hydrophilicity, crystallinity, mechanical properties and thermal stability of the fillers themselves, interface interaction, filler dispersion and thermal aspects of the composites, we concluded that the parameters responsible for such behavior were the larger aspect ratio, better dispersion and enhanced interface interaction of the CE filler. These parameters also affected the barrier properties and the process of biodegradation in soil of the composites.     

Starch-vegetable fibre composites to protect food products

The influence of wheat bran content in biodegradable composites based on cassava starch and containing glycerol and potassium sorbate were studied. Films were produced by casting and three different fractions of wheat bran fibre were used: 1.5 mg, 13.5 mg and 27.1 mg/g of matrix.It was observed that the addition of wheat bran, which contains 40 g of water insoluble fibre per 100 g of bran, shifted the glycerol-rich phase glass transition temperature toward higher temperatures, broadening and diminishing in intensity the peak associated with this relaxation. This effect suggests that the presence of fibre led to an enhancement in the glycerol dispersion.At room temperature, an increase in fibre content did not affect density of the matrix but caused the increase of the storage modulus and the decrease of loss tangent, moisture content and water vapor permeability. Besides, the addition of fibres led to the increase of the yellow index.The improvement in water vapor barrier properties jointly with the enhancement of mechanical properties when fibre was present, lead to the idea that the composite developed can be used to protect food and extend its shelf life.     

Reaction of the Co(II)-substrate radical pair catalytic intermediate in coenzyme B12-dependent ethanolamine ammonia-lyase in frozen aqueous solution from 190 to 217 K

The decay kinetics of the aminoethanol-generated Co^II-substrate radical pair catalytic intermediate in ethanolamine ammonia-lyase from Salmonella typhimurium have been measured on timescales of <10⁵ s in frozen aqueous solution from 190 to 217 K. X-band continuous-wave electron paramagnetic resonance (EPR) spectroscopy of the disordered samples has been used to continuously monitor the full radical pair EPR spectrum during progress of the decay after temperature step reaction initiation. The decay to a diamagnetic state is complete and no paramagnetic intermediate states are detected. The decay exhibits three kinetic regimes in the measured temperature range, as follows. i), Low temperature range, 190 ≤ T ≤ 207 K: the decay is biexponential with constant fast (0.57 ± 0.04) and slow (0.43 ± 0.04) phase amplitudes. ii), Transition temperature range, 207 < T < 214 K: the amplitude of the slow phase decreases to zero with a compensatory rise in the fast phase amplitude, with increasing temperature. iii), High temperature range, T ≥ 214 K: the decay is monoexponential. The observed first-order rate constants for the monoexponential (k_obs,m) and the fast phase of the biexponential decay (k_obs,f) adhere to the same linear relation on an lnk versus T⁻¹ (Arrhenius) plot. Thus, k_obs,m and k_obs,f correspond to the same apparent Arrhenius prefactor and activation energy (logA_app,f (s⁻¹) = 13.0, E_a,app,f = 15.0 kcal/mol), and therefore, a common decay mechanism. We propose that k_obs,m and k_obs,f represent the native, forward reaction of the substrate through the radical rearrangement step. The slow phase rate constant (k_obs,s) for 190 ≤ T ≤ 207 K obeys a different linear Arrhenius relation (logA_app,s (s⁻¹) = 13.9, E_a,app,s = 16.6 kcal/mol). In the transition temperature range, k_obs,s displays a super-Arrhenius increase with increasing temperature. The change in E_a,app,s with temperature and the narrow range over which it occurs suggest an origin in a liquid/glass or dynamical transition. A discontinuity in the activation barrier for the chemical reaction is not expected in the transition temperature range. Therefore, the transition arises from a change in the properties of the protein. We propose that a protein dynamical contribution to the reaction, which is present above the transition temperature, is lost below the transition temperature, owing to an increase in the activation energy barrier for protein motions that are coupled to the reaction. For both the fast and slow phases of the low temperature decay, the dynamical transition in protein motions that are obligatorily coupled to the reaction of the Co^II-substrate radical pair lies below 190 K.     

Synthesis and characterization of 2-quinoxalinol Schiff-base metal complexes

The reaction of uranyl acetate with (2,2′-(1E,1′E)-(2-benzyl-3-hydroxyquinoxaline-6,7-diyl)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene) diphenol) (H₂L1) at room temperature in methanol and chloroform yields the UO₂L1 complex. Crystals were grown through solvent diffusion of the ligand-metal complex in dimethyl formamide with diethyl ether to prepare: UO₂L1 · DMF (1). Complexes with 2,2′-(1E,1′E)-(2-benzyl-3-hydroxyquinoxaline-6,7-diyl)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)dibenzene-1,4-diol (H₂L2) and 2,2′-(1E,1′E)-(2-hydroxy-3-isopropylquinoxaline-6,7-diyl)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)diphenol (H₂L3) were also prepared, and crystals of the uranyl complexes (UO₂L2 · DMF (2) and (3)) grown from DMF/ether. A fourth complex UO₂L4 · H₂O (4) was prepared through layering a solution of the tetra-tert-butyl substituted 2-quinoxalinol salen ligand H₂L4 in acetone with an aqueous solution containing uranyl acetate. The complexes exhibit a symmetric core featuring a slightly distorted bicapped pentagonal geometry around the uranium center with two oxo-groups and two imine groups from the ligand chelating the ligand and the fifth site in the coordination plane of the ligand occupied by a solvent molecule. These compounds have been characterized using solution (NMR and UV-Vis) and solid-state (IR, X-ray crystallography) techniques. Complexes of H₂L4 with early transition metals; Mn²⁺, Co²⁺, Ni²⁺, and Cu²⁺ are also prepared and characterized for comparison of solution and spectroscopic characteristics.     

Effects of ether vs. ester linkage on lipid bilayer structure and water permeability

The structure and water permeability of bilayers composed of the ether-linked lipid, dihexadecylphosphatidylcholine (DHPC), were studied and compared with the ester-linked lipid, dipalmitoylphosphaditdylcholine (DPPC). Wide angle X-ray scattering on oriented bilayers in the fluid phase indicate that the area per lipid A is slightly larger for DHPC than for DPPC. Low angle X-ray scattering yields A = 65.1 Å² for DHPC at 48 °C. LAXS data provide the bending modulus, K_C = 4.2 × 10⁻¹³ erg, and the Hamaker parameter H = 7.2 × 10⁻¹⁴ erg for the van der Waals attractive interaction between neighboring bilayers. For the low temperature phases with ordered hydrocarbon chains, we confirm the transition from a tilted L_β′ gel phase to an untilted, interdigitated L_βI phase as the sample hydrates at 20 °C. Our measurement of water permeability, P_f = 0.022 cm/s at 48 °C for fluid phase DHPC is slightly smaller than that of DPPC (P_f = 0.027 cm/s) at 50 °C, consistent with our triple slab theory of permeability.