Soluble Polyimides from a New Dianhydride: 5′‐tert‐Butyl‐m‐terphenyl‐3,4,3″,4″‐tetracarboxylic Acid Dianhydride

A novel tert‐butyl‐containing dianhydride was prepared from readily available reagents. It was reacted with various aromatic diamines to prepare a set of polyimides containing tert‐butyl pendent groups. The resulting polyimides exhibit high molecular weights (high inherent viscosity), and a combination of desirable properties, such as good solubility in aprotic amide solvents and cresols, high glass transition temperatures (up to 320 °C), high thermal resistance, film‐forming capability and good mechanical properties.

     

Fatty acid profile of different species of algae of the Cystoseira genus: a nutraceutical perspective

The fatty acid (FA) composition of six macroalgae from the Cystoseira genus, namely Cystoseira compressa, Cystoseira humilis, Cystoseira tamariscifolia, Cystoseira nodicaulis, Cystoseira baccata and Cystoseira barbata, was determined. Polyunsaturated fatty acids (PUFA) corresponded to 29–46% of the total FA detected. C. compressa, C. tamariscifolia and C. nodicaulis stood out for their low PUFA/saturated fatty acid, low n-6 PUFA/n-3 PUFA ratios as well as favourable unsaturation, atherogenicity and thrombogenicity indices, suggesting a high nutritional value with potential applications in the nutraceutical industry.     

Physicochemical characterisation and radical-scavenging activity of Cucurbitaceae seed oils

Oils extracted from Cucurbitaceae seeds were characterised for their fatty acid and tocopherol compositions. In addition, some physicochemical characteristics, total phenolic contents and the radical-scavenging activities were determined. Oil content amounted to 23.9% and 27.1% in melon and watermelon seeds, respectively. Physicochemical characteristics were similar to those of other edible oils and the oils showed significant antioxidant activities. Fatty acid composition showed total unsaturated fatty acid content of 85.2–83.5%, with linoleic acid being the dominant fatty acid (62.4–72.5%), followed by oleic acid (10.8–22.7%) and palmitic acid (9.2–9.8%). The oils, especially watermelon seed oil, showed high total tocopherol and phenolic contents. The γ-tocopherol was the predominant tocopherol in both oils representing 90.9 and 95.6% of the total tocopherols in melon and watermelon seed oils, respectively. The potential utilisation of melon and watermelon seed oils as a raw material for food, chemical and pharmaceutical industries appears to be favourable.     

Synthesis,Crystal Structure and Magnetic Properties of a Novel Heterobimetallic Rhenium(IV)–Dysprosium(III) Chain

The use of the mononuclear rhenium(IV) precursor [ReBr₅(H₂pydc)]^? (H₂pydc=3,5‐pyridinedicarboxylic acid) as a metalloligand towards dysprosium(III) afforded the first heterobimetallic Re^IV–Dy^III complex. Crystal structures and static and dynamic magnetic properties of both rhenium‐containing species are reported herein. The 5d–4f compound shows an extended 1D structure and the AC magnetic measurements reveal frequency dependence at low temperature suggesting slow relaxation of the magnetization.     

Multiclass Compatible Sample Preparation for UHPLC–MS/MS Determination of Aflatoxin M1 in Raw Milk

A sample preparation method for aflatoxin M1 (AFM1) determination in raw milk was optimized following the quick, easy, cheap, effective, rugged and safe (QuEChERS) strategy, as an alternative to the classic immunoaffinity column clean-up (IAC). The method was adapted to address the complexity of the milk matrix, and to be suitable for final determination by ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC–MS/MS). This approach proved also to be compatible with the simultaneous extraction of pesticide residues and other contaminants (mycotoxins). Regarding AFM1, satisfactory linearity was achieved and appropriate sensitivity was maintained, using matrix-matched calibration to compensate for the heavy ion suppression. The accuracy and precision, which were determined through recovery studies, were 70–95 %, with the relative standard deviation below 15 % in all of the cases. The limit of detection (LOD, 0.002 μg L⁻¹) and limit of quantification (0.007 μg L⁻¹) are compatible with current worldwide regulations (maximum levels of 0.5 and 0.05 μg L⁻¹). The procedure was applied to samples that were naturally contaminated with a range of AFM1 at LOQ–0.187 μg L⁻¹, with comparable results to IAC clean-up, which was employed as a reference method. Therefore, AFM1 determination in raw milk by UHPLC–MS/MS detection through the present QuEChERS extraction constitutes a reliable alternative to IAC clean-up and exhibits advantages related to cost, accessibility of materials and simplicity of operation.

     

Application of the generalised SAFT-VR approach for long-ranged square-well potentials to model the phase behaviour of real fluids

In a recent generalisation of the SAFT-VR equation of state the method was extended so as to deal with short as well as long square-well ranges, namely, 1.2≤λ≤3.0$1.2\le \lambda \le 3.0$ [B.H. Patel, H. Docherty, S. Varga, A. Galindo, G.C. Maitland., Mol. Phys. 103 (1) (2005) 129–139]. Here, we confirm the accuracy of the approach by comparison with numerical calculations of the first perturbation term and with vapour pressure and coexistence density computer simulation data. The approach is then used to model a number of real substances, from non-polar to strongly polar. We discuss in particular the values of the square-well potential model found. For this purpose we construct a relative least squares objective function and the percentage absolute average deviation (%AAD) to determine the intermolecular model parameters (m  , λ$\lambda$, σ$\sigma$, ?/_kB$?/k_B$, _?hb/_kB${?}_{hb}/k_B$ and _rc$r_c$) by comparison to experimental vapour-pressure and saturated liquid density data. In order to ensure in each case that the global minimum is identified, the dimensionality of the problem is reduced by discretising the parameter-space [G.N.I. Clark, A.J. Haslam, A. Galindo, G. Jackson., Mol. Phys. 104 (22–24) (2006) 3561–3581]. Applying this method to the study of argon, n  -alkanes, nitrogen, benzene, carbon dioxide, carbon monoxide, the refrigerant R1270, hydrogen chloride hydrogen bromide and water we find that the optimal models always present square-well ranges λ<1.8$\lambda <1.8$, meaning that an upper bound value of λ=1.8$\lambda =1.8$ set in the original approach is sufficient to model real fluids; even polar ones. This finding is explained in terms of the averaged dipole–dipole interaction and of the long-range mean-field limit of the square-well potential.     

Obtaining nanocomposites of polyamide 6 and cellulose whiskers via extrusion and injection molding

Nanocomposites of polyamides with cellulose whiskers are difficult to obtain by conventional processing of extrusion and injection molding because of the low thermal stability of the cellulosic nanostructures and the relatively high processing temperature of polyamides, which is higher than the temperature of thermal degradation of cellulose whiskers. Thus, in this study cellulose whiskers were coated with polyamide 6 (PA6) in order to increase their thermal stability and prevent the formation of agglomerates. This coating on cellulose whiskers allows their application to obtain nanocomposites with polyamides, whose processing temperatures are relatively high, around 250 °C. Cellulose whiskers (CWs) were obtained from cotton fibers by acid hydrolysis. The freeze-dried CWs were coated with PA6 by dispersing them in formic acid; PA6 was solubilized in this suspension. The cellulose-coated whiskers (CCWs) were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electron microscopy (SEM-FEG) and infrared spectroscopy. SEM-FEG and TG results showed that the PA6 coating on CWs prevented high agglomeration of dried CWs and promoted an increase in their thermal stability from 180 to 280 °C, allowing the use of CCWs to obtain nanocomposites with PA6 using conventional processing routes, such as extrusion and injection molding, at appropriate processing temperatures. In this way, 1 wt% CCWs was used to prepare nanocomposites with PA6. The PA6 + 1CW nanocomposites were compared to neat PA6 without CWs. The samples were characterized by tensile tests and DSC, and the results showed that the PA6 coating on CWs was effective in raising the thermal stability of CWs, improving the dispersion of CWs in the matrix of PA6, resulting in a 45 % increase in the elastic modulus of the nanocomposite with only 1 wt% of coated cellulose whiskers in comparison to neat PA6.     

Synthetic Polyester from Algae Oil

Current efforts to technically use microalgae focus on the generation of fuels with a molecular structure identical to crude oil based products. Here we suggest a different approach for the utilization of algae by translating the unique molecular structures of algae oil fatty acids into higher value chemical intermediates and materials. A crude extract from a microalga, the diatom Phaeodactylum tricornutum, was obtained as a multicomponent mixture containing amongst others unsaturated fatty acid (16:1, 18:1, and 20:5) phosphocholine triglycerides. Exposure of this crude algae oil to CO and methanol with the known catalyst precursor [{1,2‐(tBu₂PCH₂)₂C₆H₄}Pd(OTf)](OTf) resulted in isomerization/methoxycarbonylation of the unsaturated fatty acids into a mixture of linear 1,17‐ and 1,19‐diesters in high purity (>99 %). Polycondensation with a mixture of the corresponding diols yielded a novel mixed polyester‐17/19.17/19 with an advantageously high melting and crystallization temperature.     

In vitro antibacterial and time-kill assay of ethanolic extract of Davilla nitida bark on multidrug resistant bacteria isolated from diabetic foot lesions

This study reported the antimicrobial activity of the bark extract of Davilla nitida on multidrug resistant bacteria isolated from Diabetic Foot Infections. Antibacterial activity of the bark extract was evaluated by agar Disk-Diffusion (DD), Broth Dilution (BD), Checkerboard and Time-kill methods. The extract showed a significant antibacterial activity against all groups of bacteria tested. BD was more sensitive for determining the antibacterial activity of the bark extract than the DD method. The bark extract inhibited the growth of bacteria with high-levels of antibiotic-resistance, such as Pseudomonas spp. (100.0%), Enterobacer spp. (88.89%), Staphylococcus aureus (54.55%), Streptococcus pneumoniae (75.0%), Staphylococcus saprophyticus (92.86%). The combination of extract with antibiotics resulted in an additive effect against most of the strains tested. Time-kill kinetics profiles of bark extract showed bactericidal and time-dependent properties. Our results suggest that the bark extract of Davilla nitida is a source of bioactive compounds, which may be useful against antibiotic-resistant bacteria.     

Thermodynamics of partitioning of benzocaine in some organic solvent/buffer and liposome systems

The thermodynamics of partitioning of benzocaine (BZC) were studied in octanol/buffer (ROH/W), isopropyl myristate/buffer (IPM/W), cyclohexane/buffer (CH/W), and dimyristoyl phosphatidylcholine (DMPC) and dipalmitoyl phosphatidylcholine (DPPC) liposome systems. In all cases the partition coefficients were greater than unity; therefore the free energies of transfer were negative, that is, the processes of transfer of BZC from aqueous media to organic systems were spontaneous. The partition coefficients were approximately three-fold higher in DMPC liposomes compared with the ROH/W system in the 30 degrees -40 degrees C temperature range. The enthalpies of transfer from aqueous media to ROH and IPM were negative, but positive for CH, while this property was negative for DMPC liposomes and positive for DPPC liposomes. The entropies of transfer were positive in almost all cases, except for DMPC. The results presented here confirm the lipophilic nature of BZC.