Novel ethero atoms containing polyesters based on 2,6‐naphthalendicarboxylic acid: A comparative study with poly(butylene naphthalate)

Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the T_g value, a decrement of T_m, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007     

Charge-transfer complexes as polymerization inhibitors. I. Amine–chloranil complexes as inhibitors for the radical polymerization of methyl methacrylate

Charge-transfer complexes of N,N-dimethylaniline (DMA) and triethylamine (TEA) with chloranil have been investigated as inhibitors for the sensitized polymerization of methyl methacrylate (MMA) in bulk and in solution. Complete inhibition is achieved by the complexes of both amines followed by retardation only in case of DMA. The higher inhibiting efficiency of the TEA complexes is attributed to their greater stability. The polymers formed in the presence of chloranil alone or its complexes with both amines are quinonoid and contain no combined nitrogen. The results support the idea that inhibition reaction involve electron transfer from the growing chains to the quinone, with formation of molecular complexes of polymeric cations and semiquinone anions. The latter are the actual inhibiting species, so that the efficiency of inhibiting depends on their concentration, which is determined by the stability of the molecular complexes formed. The inhibition reactions should accordingly be considered as oxidation–reduction processes in which the growing chains are the electron donors. The suggested mechanism affords an explanation for the great differences in the inhibiting power of a particular quinone for the polymerization of different monomers.     

Energetic Bio-Activation of Some Organic Molecules and Their Antioxidant Activity in the Pulp of the Moroccan Argan Tree «Argania spinosa L.»

Argania spinosa L. Skeels is an emblematic tree in Morocco, known worldwide for its medicinal and nutritional value. Its fruits contain kernels used to prepare an edible oil, the leaves are used to feed livestock, and its wood is used as fuel. If the oil acquires high importance, the other components of the fruit of the argan are undervalued. Our objective is to invest the waste of the argan industry. Particularly, our study aimed to assess the effect of thermal activation of argan pulp on its therapeutic value, its phenolic profile and its functional and physicochemical properties. After heat treatment, the HPLC analysis for the average total phenolic content varied from 2% to 37%, depending on temperature. The antioxidant activity was increased with heat treatment. Higher values of antioxidant activity, polyphenol and pigment content were recorded at 70 °C. Functional properties analysis indicated that water solubility index and water absorption capacity were significantly affected by heat stress. Physicochemical analysis showed that moisture content, titratable acidity and soluble solids were affected.     

Trichoderma Enzymes for Degradation of Aflatoxin B1 and Ochratoxin A

The contamination of agricultural products with mycotoxins causes risks to animal and human health and severe economic losses. Mycotoxicoses can be reduced by preventing fungal infection using chemical and biological approaches. The chemical strategies can release toxic molecules; therefore, strategies for biological control are being evaluated, such as using nontoxic fungi and their metabolites. This work evaluated the effect of exoenzymes produced by the beneficial fungus Trichoderma afroharzianum strain T22 in degrading Aflatoxin B1 (AFB1) and Ochratoxin A (OTA). The ability of Trichoderma to produce hydrolases was stimulated by using different inducing substrates. The highest AFB1 and OTA degradation activity was obtained using a medium containing lyophilized mushrooms and crude fiber. The T. afroharzianum T22’s ability to reduce mycotoxins may be attributed to peroxidase enzymes. This study showed that T. afroharzianum strain T22 or its peroxidase supplementation could represent a sustainable strategy for the degradation of AFB1 and OTA in feed and food products.     

Nano-Structured Ridged Micro-Filaments (≥100 µm Diameter) Produced Using a Single Step Strategy for Improved Bone Cell Adhesion and Proliferation in Textile Scaffolds

Textile scaffolds that are either 2D or 3D with tunable shapes and pore sizes can be made through textile processing (weaving, knitting, braiding, nonwovens) using microfilaments. However, these filaments lack nano-topographical features to improve bone cell adhesion and proliferation. Moreover, the diameter of such filaments should be higher than that used for classical textiles (10–30 µm) to enable adhesion and the efficient spreading of the osteoblast cell (>30 µm diameter). We report, for the first time, the fabrication of biodegradable nanostructured cylindrical PLLA (poly-L-Lactic acid) microfilaments of diameters 100 µm and 230 µm, using a single step melt-spinning process for straightforward integration of nano-scale ridge-like structures oriented in the fiber length direction. Appropriate drawing speed and temperature used during the filament spinning allowed for the creation of instabilities giving rise to nanofibrillar ridges, as observed by AFM (Atomic Force Microscopy). These micro-filaments were hydrophobic, and had reduced crystallinity and mechanical strength, but could still be processed into 2D/3D textile scaffolds of various shapes. Biological tests carried out on the woven scaffolds made from these nano-structured micro filaments showed excellent human bone cell MG 63 adhesion and proliferation, better than on smooth 30 µm- diameter fibers. Elongated filopodia of the osteoblast, intimately anchored to the nano-structured filaments, was observed. The filaments also induced in vitro osteogenic expression, as shown by the expression of osteocalcin and bone sialoprotein after 21 days of culture. This work deals with the fabrication of a new generation of nano-structured micro-filament for use as scaffolds of different shapes suited for bone cell engineering.     

Antioxidant and Gastroprotective Activity of Suaeda fruticosa Forssk. Ex J.F.Gmel

Suaeda fruticosa Forssk. Ex J.F.Gmel is traditionally used for inflammatory and digestive disorders, as a carminative, and for diarrhea. This plant is widely distributed in Asia, Africa, and the Mediterranean region. Aqueous methanolic extract of S. fruticosa (Sf.Cr) was prepared and screened for phytoconstituents through qualitative and GC-MS analysis. Quantification of total phenolic and flavonoid contents was performed, while antioxidant capacity was determined by DPPH, CUPRAC, FRAP, and ABTS assays. The gastroprotective activity was assessed in an ethanol-induced ulcer model. Gastric secretory parameters and macroscopic ulcerated lesions were analyzed and scored for ulcer severity. After scoring, histopathology was performed, and gastric mucus contents were determined. Oral pre-treatment of Sf.Cr demonstrated significant gastroprotection. The gastric ulcer severity score and ulcer index were reduced while the %-inhibition of ulcer was increased dose-dependently. The Sf.Cr significantly elevated the pH of gastric juice, while a decrease in total acidity and gastric juice volume was observed. Histopathology demonstrated less oedema and neutrophil infiltration in gastric mucosa of rats pre-treated with the Sf.Cr in comparison to ethanol-intoxicated animals. Furthermore, the gastric mucus contents were increased as determined by alcian blue binding. Sf.Cr showed marked gastroprotective activity, which can be attributed to antioxidant, antisecretory, and cytoprotective effects.     

Permutation Entropy-Based Interpretability of Convolutional Neural Network Models for Interictal EEG Discrimination of Subjects with Epileptic Seizures vs. Psychogenic Non-Epileptic Seizures

The differential diagnosis of epileptic seizures (ES) and psychogenic non-epileptic seizures (PNES) may be difficult, due to the lack of distinctive clinical features. The interictal electroencephalographic (EEG) signal may also be normal in patients with ES. Innovative diagnostic tools that exploit non-linear EEG analysis and deep learning (DL) could provide important support to physicians for clinical diagnosis. In this work, 18 patients with new-onset ES (12 males, 6 females) and 18 patients with video-recorded PNES (2 males, 16 females) with normal interictal EEG at visual inspection were enrolled. None of them was taking psychotropic drugs. A convolutional neural network (CNN) scheme using DL classification was designed to classify the two categories of subjects (ES vs. PNES). The proposed architecture performs an EEG time-frequency transformation and a classification step with a CNN. The CNN was able to classify the EEG recordings of subjects with ES vs. subjects with PNES with 94.4% accuracy. CNN provided high performance in the assigned binary classification when compared to standard learning algorithms (multi-layer perceptron, support vector machine, linear discriminant analysis and quadratic discriminant analysis). In order to interpret how the CNN achieved this performance, information theoretical analysis was carried out. Specifically, the permutation entropy (PE) of the feature maps was evaluated and compared in the two classes. The achieved results, although preliminary, encourage the use of these innovative techniques to support neurologists in early diagnoses.     

Kinetic study on effect of novel cationic dimeric surfactants for the cleavage of carboxylate ester

Kinetic study has been performed to understand the reactivity of novel cationic gemini surfactants viz. alkanediyl‐α,ω‐bis(hydroxyethylmethylhexadecylammonium bromide) C₁₆‐s‐C₁₆ MEA, 2Br^? (where s = 4, 6) in the cleavage of p‐nitrophenyl benzoate (PNPB). Novel cationic gemini C₁₆‐s‐C₁₆ MEA, 2Br^? surfactants are efficient in promoting PNPB cleavage in presence of butane 2,3‐dione monoximate and N‐phenylbenzohydroxamate ions. Model calculation revealed that the higher catalytic effect of ethanol moiety of gemini surfactants (C₁₆H₃₃N⁺ C₂H₄OH CH₃ (CH₂)_S N⁺ C₂H₄OH CH₃C₁₆H₃₃, 2Br^?, s = 4, 6) is due to their higher binding capacity toward substrate. This is in line with finding that binding constants for novel series of cationic gemini surfactants are higher than conventional cationic gemini (C₁₆H₃₃N⁺(CH₃)₂(CH₂)_SN⁺(CH₃)₂C₁₆H₃₃, 2Br^?, s = 10, 12), cetyldimethylethanolammonium bromide and zwitterionic surfactants, i.e. C_nH_2n+1N⁺Me₂ (CH₂)₃ SO₃^? (n = 10; SB3‐10). The fitting of kinetic data was analyzed by the pseudophase model. Copyright © 2013 John Wiley & Sons, Ltd.     

Second-order subdifferentials of C1,1 functions and optimality conditions

We present second-order subdifferentials of Clarke's type of C ^1,1 functions, defined in Banach spaces with separable duals. One of them is an extension of the generalized Hessian matrix of such functions in ⁿ , considered by J. B. H.-Urruty, J. J. Strodiot and V. H. Nguyen. Various properties of these subdifferentials are proved. Second-order optimality conditions (necessary, sufficient) for constrained minimization problems with C ^1,1 data are obtained.This work was partially supported by the National Foundation for Scientific Investigations in Bulgaria under contract No. MM-406/1994.     

A combined crossed molecular beam and quasiclassical trajectory study of the Titan-relevant N(2D) + D2O reaction

Following a recent investigation on the N(²D) + H₂O reaction [Homayoon et al., J. Phys. Chem. Lett. 5, 3508 (2014)], we report on an experimental and theoretical study of the isotopologue N(²D) + D₂O reaction. Crossed molecular beam (CMB) experiments were conducted at a collision energy of 10.3 kcal mol^–1. Quasiclassical trajectory calculations were performed on a recent potential energy surface to derive the centre-of-mass functions necessary to simulate the CMB laboratory distributions. Excellent agreement was found. The importance of the channel leading to HON/DON was confirmed. The inclusion of this channel, in addition to that leading to the isomer HNO/DNO, can affect the models considering the coupling between nitrogen and oxygen chemistry in the upper atmosphere of Titan.