Optimization of antioxidant hydrolysate production from flying squid muscle protein using response surface methodology

The squid muscle protein, extracted from by-products of flying squid (Ommastrephes bartrami) was hydrolyzed by five proteases (pepsin, trypsin, papain, alcalase and flavourzyme). DPPH radical scavenging power was used to evaluate antioxidative activity of hydrolysates. The hydrolysate obtained by papain exhibited the most excellent potential of antioxidative activity. Furthermore, response surface methodology (RSM) was employed to optimize hydrolysis conditions, including enzyme to substrate (E/S) ratio, reaction temperature, and hydrolysis time. The optimum conditions obtained were as follows: E/S ratio of 1.74%, temperature of 51 °C and time of 46 min, under which, DPPH radical scavenging activity of 74.25% was obtained. Moreover, it was found that the optimum hydrolysate of 8 mg/mL displayed relatively stronger inhibitory effect on lipid peroxidation compared with α-Tocopherol of 0.1 mg/mL.     

Design and characterization of modified urethane lacquer coating

A new series of natural lacquer/polyurethane (LPU) blended films were synthesized. The new lacquer/polyurethane films have very good visual color and detected gloss, fast drying time, strong weather resistance, especially against UV light and water, and a better pencil lead hardness (8H). The gel ratio increases with drying time and becomes stable after 6 months (more than 99%). The surface glass transition temperature (T_gs) obtained from a rigid-body pendulum physical properties testing (RPT) instrument showed that the new LPU films dried for 6 months have higher T_gs than polyurethane (PU) films in the following order: LPU 100 > LPU 90 > LPU 80 > LPU 70 > LPU 60 > LPU 50 > PU. Differential scanning calorimeter (DSC) results showed the same tendency as T_g but without a great gap in the LPU series except for polyurethane. Thermogravimetric analysis (TGA) showed that when the ratio of natural lacquer is more than 50%, the 50% weight loss temperatures increase about 100 °C. In addition, the reaction between lacquer and polyurethane is discussed based on the IR and NMR measurements.     

Preparation of waterborne polyurethanes using an amphiphilic diol for breathable waterproof textile coatings

The application of polyurethanes (PUs) on breathable waterproof fabric coatings requires a balance of water vapor permeability (WVP) and water resistance which can be achieved by tailoring hydrophilic and hydrophobic segments. PU prepolymers were prepared from isophorone diisocyanate, dimethylol butanoic acid, and a mixture of various ratios of amphiphilic PPG2050 (copolymer of ethylene oxide and propylene oxide with –OH end groups) and hydrophobic poly(tetramethylene ether glycol) (PTMEG). After neutralization with triethylamine, the prepolymers were chain-extended with ethylene diamine/1,4-butanediol (1:1 by molar). The WVP values of the fabric coatings prepared using various waterborne PUs were very similar (910–990 g/m² × 24 h). When waterborne PUs prepared using a mixture of PPG2050 and PTMEG were employed for the textile coatings, the resulting PU-coated textiles exhibited excellent waterproof properties (>10,000 mm H₂O). The textile coatings prepared from PPG2050/PTMEG-based waterborne PUs were significantly more waterproof than those prepared from poly(ethylene glycol) (PEG)/poly(propylene glycol) (PPG)/PTMEG-based waterborne PU. This is probably due to a more even distribution of hydrophobic segments in the PUs, even though the WVP values of the PEG/PPG/PTMEG-based PU coatings were considerably smaller than those of the PPG2050/PTMEG-based PU coatings.     

Structure of segmented poly(ether urethane)s containing amino and hydroxyl functionalized polyhedral oligomeric silsesquioxanes (POSS)

Polyhedral oligomeric silsesquioxanes (POSS) with an empirical formula [RSiO_1.5]_n (where n = 6, 8,…14, and R is a reactive organic group) represent a new type of nanomodifiers for polyurethanes (PUs) to produce organic–inorganic hybrids (OIHs), which are promising candidates for modern applications spreading from biomedical to airspace technologies. In this paper we report on the synthesis and structural organization of two different series of PU–POSS copolymers (branched and cross-linked) based on a mixture of variable size oligomeric silsesquioxanes (POSS-M) of a general formula [(HOCH₂CH(OH)CH₂)₂N(CH₂)₃SiO_1,5]_n. Chemical structure of the synthesized POSS-M containing PUs has been confirmed by gel permeation chromatography and IR spectroscopic studies. Complex several-level hierarchy of their physical structural organization could be recognized from small angle X-ray scattering (SAXS) and atomic force microscopic (AFM) studies. SAXS experiments revealed that processes of microphase segregation and formation of nano-sized domains enriched with the inorganic phase (POSS fragments) take place during synthesis of the OIH systems. These nano-heterogeneity regions contain up to 66 vol.% of SiO_1.5 and form a paracrystalline lattice with hexagonal symmetry and characteristic interplanar periodicity of around 15 nm. The average size of inorganic phase nano-inclusions can be estimated as 2–3 nm, which corresponds to several POSS moieties in size. Cross-linked POSS-M containing PUs, as topologically more complex systems, is characterized with a diffusion-limited microphase segregation features. In the latter case the regions of nano-heterogeneity are smaller in size, have smaller content of the inorganic phase (ca. 54 vol.%), and form a less perfect paracrystalline order with the periodicity of 9.7 nm. Generally, we demonstrate that replacement of regular POSS moieties with the mixed POSS-M ones can lead to nanocomposite systems with an ordered supramolecular structural organization and simultaneous reduction of their production cost due to relative simplicity of their synthesis.     

Enhanced ferroelectric properties of La-substituted BiFeO3 thin films on LaSrCoO3/Pt/TiO2/SiO2/Si (1 0 0) substrates prepared by the soft chemical method

Bi_0.85La_0.15FeO₃ (BLFO015) thin films were deposited by the polymeric precursor solution on La_0.5Sr_0.5CoO₃ substrates. For comparison, the films were also deposited on Pt bottom electrode. X-ray diffraction data confirmed the substitutions of La into the Bi site with the elimination of all secondary phases under a substitution ratio x = 15% at a temperature of 500 °C for 2 h. A substantial increase in the remnant polarization (P_r) with La_0.5Sr_0.5CoO₃ bottom electrode (P_r ≈ 34 μC/cm²) after a drive voltage of 9 V was observed when compared with the same film deposited on Pt substrate. The leakage current behavior at room temperature decreased from 10^?8 (Pt) to 10^?10 A/cm² on (La_0.5Sr_0.5CoO₃) electrode under a voltage of 5 V. The fatigue resistance of the Au/BLFO015/LSCO/Pt/TiO₂/SiO₂/Si (1 0 0) capacitors with a thickness of 280 nm exhibited no degradation after 1 × 10⁸ switching cycles at a frequency of 1 MHz.     

Photocatalytic degradation of acetic acid on spinel ferrites MFe2O4 (M = Mg,Zn, and Cd)

Spinel ferrites MFe₂O₄(M = Mg, Zn, and Cd) with Fe(III) in a d⁵ electron configuration were prepared via a conventional solid-state reaction. The amount of CO₂ generated by the photocatalytic degradation of acetic acid on these ferrites was measured under irradiation by a xenon lamp with a power of 300 W. Photocatalytic degradation was observed for all the compounds, and the results revealed that MgFe₂O₄ exhibited the highest degradation, i.e., 196 μmol/g/h. The degradation in the presence of MFe₂O₄(M = Mg, Zn, and Cd) increased with increasing heating condition.     

Pervaporation separation of benzene/cyclohexane through AAOM-ionic liquids/polyurethane membranes

Supported ionic liquids/polyurethane (PU) membranes were prepared by immobilizing ionic liquids on a porous anodic aluminum oxide membrane (AAOM) support that was coated on one side with polyurethane (PU). The microstructure of all membranes was characterized using scanning electron microscopy (SEM). The pervaporation separation performance of the supported ionic liquids/polyurethane membranes was investigated for benzene/cyclohexane (Bz/Cy) mixtures. The SEM results demonstrated that the porous surface of the AAOM support was sealed by the dense polyurethane membrane and the pores of the AAOM support were impregnate with ionic liquids. The ionic liquids filling in the AAOM support enhanced the separation selectivity of Bz/Cy. The separation factor of Bz to Cy increased from 5 to 34.4 and the largest PSI of AAOM-[C₄mim]PF₆/PU membrane reached 452.54 g m⁻² h⁻¹ at 55 °C for a 50 wt.% Bz/Cy mixture. Because the polyurethane prevented the leakage of ionic liquids filled in the AAOM support, the supported ionic liquids/polyurethane membranes exhibited excellent stability.     

Synthesis and characterization of a cross-linkable nonlinear optical polymer functionalized with a thiophene- and tricyanovinyl-containing chromophore

This paper reports a novel nonlinear optical polymer BP-AVT-TCV functionalized with a thiophene- and tricyanovinyl-substituted chromophore. BP-AVT-TCV was synthesized by the post-tricyanovinylation of an epoxy-based precursor polymer BP-AVT, and had a high molar functionalization degree of chromophore (70 mol.%). It had an enhanced glass transition temperature (T_g = 164 °C) compared with BP-AVT (T_g = 114 °C), and a high decomposition temperature (T_d,5% = 295 °C). BP-AVT-TCV was further cross-linked to achieve the three-dimensional (3D) network of thermosetting polyurethane (PU). The poled PU films revealed an electro-optic (EO) coefficient (γ₃₃) value of 21 pm/V at a wavelength of 1315 nm. The structures of the polymers were confirmed by FT-IR, UV–Vis, and ¹H NMR spectra.     

The effect of sintering temperature and time on microwave properties of Sm(Zn1/2Ti1/2)O3 ceramics for resonators

The microwave dielectric properties of Sm(Zn_1/2Ti_1/2)O₃ ceramics have been investigated. Sm(Zn_1/2Ti_1/2)O₃ ceramics were prepared by conventional solid-state route with various sintering temperatures and times. The prepared Sm(Zn_1/2Ti_1/2)O₃ exhibited a mixture of Zn and Ti showing 1:1 order in the B-site. Higher sintered density of 7.01 g/cm³ can be produced at 1310 °C for 2 h. The dielectric constant values (ɛ_r) of 22–31 and the Q × f values of 4700–37,000 (at 8 GHz) can be obtained when the sintering temperatures are in the range of 1250–1370 °C for 2 h. The temperature coefficient of resonant frequency τ_f was a function of sintering temperature. The ɛ_r value of 31, Q  ×  f value of 37,000 (at 8 GHz) and τ_f value of −19 ppm/°C were obtained for Sm(Zn_1/2Ti_1/2)O₃ ceramics sintered at 1310 °C for 2 h. For applications of high selective microwave ceramic resonator, filter and antenna, Sm(Zn_1/2Ti_1/2)O₃ is proposed as a suitable material candidate.     

Production and characterization of chitosan microparticles containing papain for controlled release applications

The production and modification of chitosan microparticles using crosslinking agents and papain were evaluated for controlled release applications. Chitosan microparticles were produced and crosslinked with sodium tripolyphosphate (TPP) 10% (w/v) solution or glutaraldehyde (GLU) 0.75% (w/w), with subsequent papain sorption. Microparticles were characterized by Fourier transformed infrared spectroscopy (FTIR) for chemical modifications, scanning electron microscopy (SEM) for morphology and X-ray diffraction (XRD) for crystallographic analysis. Chemical composition and the thermal stability of the material were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It was observed that the presence of TPP and papain resulted in a decrease of the stability of the chitosan matrix. Papain release rates from the microparticles were also conducted in vitro. The amount of released papain in phosphate buffer (pH = 7.4) was analyzed with UV-spectroscopy, showing release profiles of enzymatic activity ranging from 0.006 to 0.011 μmol.min^? 1. The results indicate that both chitosan–TPP–papain and chitosan–GLU–papain microparticles can successfully be used for systems that aim at a controlled release of papain with potential use in the biomedical area.     

Microwave dielectric properties of (Zn1/3B2/3)0.5(Ti0.8M0.2)0.5O2 (B = Nb5+, Ta5+, M = Sn4+, Ge4+) ceramics

Dielectric properties of (Zn_1/3Nb_(2?x)/3Ta_x/3)_0.5(Ti_0.8Sn_0.1Ge_0.1)_0.5O₂ (x = 0, 1, 2) and/or (Zn_1/3Nb_1/3Ta_l/3)_0.5(Ti_0.8Sn_0.2(l?y)Ge_0.2y)_0.5O₂ (y = 0, 0.5, 1) were investigated at the microwave frequencies. For the compositions with single phase of rutile structure, the dielectric constant (K) of specimens was not only dependent on the dielectric polarizabilities, but also on the bond length ratio of apical bond (d_apical) to equatorial bond (d_equatorial) of oxygen octahedron in the unit cell. Temperature coefficients of the resonant frequencies (TCF) of the specimens with B = Nb⁵⁺ and/or M = Sn⁴⁺ was larger than those with B = Ta⁵⁺ and/or M = Ge⁴⁺. These results could be attributed to the changes of the degree of oxygen octahedral distortion. Quality factors (Qf) of the specimens with B = Ta⁵⁺ and/or M = Sn⁴⁺ were larger than those with B = Nb⁵⁺ and/or M = Ge⁴⁺.     

New prototype for the treatment of falling film liquid effluents by gliding arc discharge part I: Application to the discoloration and degradation of anthraquinonic Acid Green 25

Gliding arc discharge (GAD) reactors are continuously in progress in order to improve the treatment efficiency of recalcitrant compounds. However, up to now, they remain difficult to transfer to industrial applications because of some technical constraints in their design. In this study, a new efficient prototype is proposed for the treatment of gravity falling film shaped of liquid effluents. The liquid flow rate is now continuous as the tank containing the solution to be treated is replaced by an inclined plate along which flows the liquid. The various working parameters are optimized and the new prototype efficiency is tested on discolouration and degradation of the anthraquinonique Acid Green 25. The optimized values obtained are: the liquid flow rate ω = 1 L h⁻¹, the plate tilt angle α = 45° and the channel width Δ = 3 mm. The rates of discolouration and degradation reach 95% and 90% respectively after 12 cycles (180 min) of plasma exposition. The GAD in the presence of humid air generates highly oxidizing radical species such as ^•OH with a standard potential E°[(^•OH/H₂O) = 2.85 V/SHE] and its reducer agent H₂O₂ [E°(H₂O₂/H₂O) = 1.68 V/SHE.     

Microwave-enhanced catalytic degradation of phenol over nickel oxide

A mix-valenced nickel oxide, NiO_x, was prepared from nickel nitrate aqueous solution through a precipitation with sodium hydroxide and an oxidation by sodium hypochlorite. Further, pure nickel oxide was obtained from the NiO_x by calcination at 300, 400 and 500 °C (labeled as C300, C400 and C500, respectively). They were characterized by thermogravimetry (TG), X-ray diffraction (XRD), nitrogen adsorption at −196 °C and temperature-programmed reduction (TPR). Their catalytic activities towards the degradation of phenol were further studied under continuous bubbling of air through the liquid phase. Also, the effects of pH, temperature and kinds of nickel oxide on the efficiency of the microwave-enhance catalytic degradation (MECD) of phenol have been investigated. The results indicated that the relative activity affected significantly with the oxidation state of nickel, surface area and surface acidity of nickel oxide, i.e., NiO_x (>+2 and S_BET = 201 m² g⁻¹) ≫ C300 (+2 and S_BET = 104 m² g⁻¹) > C400 (+2 and S_BET = 52 m² g⁻¹) > C500 (+2 and S_BET = 27 m² g⁻¹). The introduction of microwave irradiation could greatly shorten the time of phenol degradation.     

Clean production of chloroanilines by selective gas phase hydrogenation over supported Ni catalysts

We have established for the first time 100% selectivity in the continuous gas phase hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline for reaction over a series of oxide and carbon supported Ni catalysts (6 ± 2%, w/w) under mild reaction conditions (T = 393 K, P = 1 atm). Catalyst activation by temperature programmed reduction (TPR) is addressed, BET area and H₂ uptake measurements provided and mean metal particle sizes evaluated by transmission electron micrographic (TEM) analysis. The following activity sequence has been determined: Ni/Al₂O₃ > Ni/SiO₂ > Ni/Activated Carbon > Ni/graphite. Pd/Al₂O₃, as an alternative catalyst, delivered an appreciably higher activity but with the production of nitrobenzene (principal product) and aniline (secondary product), i.e. hydrodechlorination with subsequent –NO₂ reduction prevailed. Exclusive formation of the corresponding haloaniline is also demonstrated for the hydrogenation of o-chloronitrobenzene, m-chloronitrobenzene and p-bromonitrobenzene over Ni/Al₂O₃. A lower hydrogenation rate is established for p-CNB relative to nitrobenzene, consistent with a halogen substituent deactivation effect. While the Ni catalysts suffered a loss of activity with time-on-stream, exclusive selectivity to the haloamine product was maintained. These preliminary results can serve as a basis for the development of a cleaner, high throughput production of commercially important haloamines.     

Catalytic gasification of lignin with Ni/Al2O3–SiO2 in sub/supercritical water

Lignin has been gasified with a Ni/Al₂O₃–SiO₂ catalyst in sub/supercritical water (SCW) to produce gaseous fuels. XRD pattern at 6θ angle shows characteristic peaks of crystalline NiO, NiSi, and AlNi₃, suggesting that Al₂O₃–SiO₂ not only offers high surface area (122 m² g) for Ni, but also changes the crystal morphology of the metal. 9 mmol/g of H₂ and 3.5 mmol/g of CH₄ were produced at the conditions that 5.0 wt% alkaline lignin plus 1 g/g Ni/Al₂O₃–SiO₂ operating for 30 min at 550 °C. A kinetic model was also developed, and the activation energies of gas and char formation were calculated to be 36.68 ± 0.22 and 9.0 ± 2.4 kJ/mol, respectively. Although the loss of activity surface area during reuse caused slight activity reduction in Ni/Al₂O₃–SiO₂, the catalyst system still possessed high catalytic activity in generating H₂ and CH₄. It is noted that sulfur linkage could be hydrolyzed to hydrogen sulfide in the gasification process of alkaline lignin. The stable chemical states of Ni/Al₂O₃–SiO₂ grants its insensitivity to sulfur, suggesting that Ni/Al₂O₃–SiO₂ should be economically promising for sub/supercritical water gasification of biomass in the presence of sulfur.     

Enzymatic modification of sesame seed protein,sourced from waste resource for nutraceutical application

The functional characteristics which include protein solubility at different pH, emulsifying and foaming properties, degree of hydrolysis, molecular weight distribution, antioxidant and ACE inhibitory activity of sesame protein hydrolysates prepared with pepsin, papain and alcalase enzymes were evaluated. The rate of degree of hydrolysis was found to reach maximum (25–30%) within the first time fragment i.e 10 min but 80% of hydrolysis was obtained in 120 min with alcalase. SDS-PAGE of hydrolysates with papain, pepsin and alcalase evinced bands of low molecular weight protein of 14.3 kDa and even lower for alcalase treatment of 120 min. Hydrolysates so formed were of improved functional properties as evident from emulsifying and foaming property. Hydrolysis with different proteases enhanced the protein solubility significantly at pH 7.0. Antioxidative assay revealed radical scavenging activity of the hydrolysates with papain hydrolysates showing maximum antioxidative efficacy. The ultra-filtered peptide fractions which showed comparable ACE inhibitory activity were sequenced by MALDI-TOF and matched to that of previously identified ACE inhibitory peptides. The results corroborate the ACE inhibitory effect of the peptides. Hence, these highly bioactive protein hydrolysates produced from waste sesame meals can be successfully employed in various functional food formulations.     

Annealing effect on temperature coefficient of resistivity in La1−xSrxMnO3 ceramics

We investigated annealing effects of La_1?xSr_xMnO₃ (x = 0–0.6) on electrical resistivity and the temperature coefficient of resistivity (TCR). The annealed samples’ resistivity was lower than those of non-annealed samples. For example, annealing changed the resistivity of x = 0.3 at 25 °C from 4.50 × 10^?5 to 3.71 × 10^?5 Ω m. Remarkable difference in TCR was observed after annealing, for x = 0.3, 0.45, and 0.5. For x = 0.3, the TCR after annealing was 4000 ppm/°C, which was 1250 ppm/°C greater than that before annealing. We investigated (1) crystal phase, (2) Mn average valence, (3) Mott insulator–metal transition temperature, and (4) microstructure. The microstructure was remarkably varied for annealed x = 0.3 and 0.5. The average grain size of the x = 0.3 increased from 1.60 up to 2.38 μm. Results show that annealing affects resistivity and TCR because of grain growth during annealing.     

Photodegradation of tetrahalobisphenol-A (X = Cl,Br) flame retardants and delineation of factors affecting the process

The photoassisted degradation (HPLC-UV absorption), dehalogenation (HPLC-IC) and mineralization (TOC decay) of the flame retardants tetrabromobisphenol-A (TBBPA) and tetrachlorobisphenol-A (TCBPA) were examined in UV-irradiated alkaline aqueous TiO₂ dispersions (pH 12), and for comparison the parent bisphenol-A (BPA, an endocrine disruptor) in pH 4–12 aqueous media to assess which factor impact most on the photodegradative process. Complete degradation (2.7–2.8 × 10⁻² min⁻¹) and dehalogenation (1.8 × 10⁻² min⁻¹) of TBBPA and TCBPA occurred within 2 h of UV irradiation, whereas only 45–60% mineralization (2.3–2.7 × 10⁻³ min⁻¹) was complete within 5 h for the flame retardants at pH 12 and ca. 80% for the parent BPA. Factors examined in the pH range 4–12 that impact the degradation of BPA were the point of zero charge of TiO₂ particles (pH_pzc; electrophoretic method), particle or aggregate sizes of TiO₂ (light scattering), and the relative number of OH radicals (as DMPO–OH adducts; ESR spectroscopy) produced in the UV-irradiated dispersion. Dynamics of BPA degradation (2.0–2.4 × 10⁻² min⁻¹) were pH-independent and independent of particle/aggregate size, but did correlate with the number of OH radicals, at least at pHs 4 to 8–9, after which the rates decreased somewhat at pH > 9 with decreasing adsorption owing to Coulombic repulsive forces between the very negative TiO₂ surface and the anionic forms of BPA (pK_as ca. 9.6–11.3), even though the number of OH radicals continued to increase at the higher pHs.     

Abnormal variation of microwave dielectric properties in A/B site co-substituted (Ca1−0.3xLa0.2x)[(Mg1/3Ta2/3)1−xTix]O3 complex perovskite ceramics

A/B site co-substituted (Ca_1?0.3xLa_0.2x)[(Mg_1/3Ta_2/3)_1?xTi_x]O₃ ceramics (0.1 ≤ x ≤ 0.5) were prepared by solid state reaction and the structures, microstructures and dielectric properties were investigated. B site 1:2 cation ordering and oxygen octahedra tilting lead to monoclinic symmetry with space group P2₁/c for x = 0.1. For x above 0.1, the ordering was destroyed and the crystal structure became orthorhombic with space group Pbnm. The B site 1:2 cation ordering tended to be destroyed to form 1:1 ordering by the A site La³⁺ substitution. The dielectric constant increased linearly with increasing content of Ti⁴⁺ as the increasing second Jahn–Teller distortion enhanced the B site cation rattling. The temperature coefficient of resonant frequency and Qf values showed abnormal variations, which were refined to be caused by the increasing A site cation vacancy and diffused distribution of small size ordering domains respectively. Good combination of microwave dielectric properties was obtained at x = 0.5, where ?_r = 48, Qf = 21,000 GHz and τ_f = 2.2 ppm/°C.     

The design,synthesis and nonlinear optical properties of a novel,Y-type polyurethane containing tricyanovinylthiophene of high thermal stability

A novel, Y-type polyurethane containing 1-(2,4-dioxyethoxy)phenyl-2-{5-(2,2-dicyanovinyl)-2-thiophenyl}ethenes as nonlinear optical chromophores present within the polymer backbone, was prepared and characterized. The compound was soluble in common organic solvents and displayed thermal stability up to 260 °C and a glass transition temperature (T_g) of 163 °C. The second harmonic generation coefficient (d₃₃) of poled polymer films at the compound's fundamental wavelength of 1560 nm was ～3.72 × 10^?9 esu. Dipole alignment exhibited high thermal stability up to the T_g, and there was no decay in d₃₃ below 148 °C owing to the partial main-chain character of the polymer structure.