Statics and dynamics of single chains in polymer blends and copolymer melts — results beyond the random phase approximation

We present new results on the behaviour of single chains in homo-and copolymer blends which are beyond the rendom phase approximation (RPA). The radius of gyration of a chain in the blend was found to depend strongly on the interactions as well as the effective diffusion constant of a single chain in the blend or copolymer melt. Note that these results cannot be obtained in the original formulation of the RPA. They are based on the effective Hamiltonian of the chain in the medium. In the equation found for the self diffusion constant of a single chain, D_s, the second term is directly the value of the effective potential at zero wave vector. Thus the measurement of D_s would detect the screened potential at q = 0. Experimental verification of these results is in progress.     

Hibernation impact on the catalytic activities of the mitochondrial D-3-hydroxybutyrate dehydrogenase in liver and brain tissues of jerboa (<Emphasis Type="Italic">Jaculus orientalis</Emphasis>)

Background

Jerboa (Jaculus orientalis) is a deep hibernating rodent native to subdesert highlands. During hibernation, a high level of ketone bodies i.e. acetoacetate (AcAc) and D-3-hydroxybutyrate (BOH) are produced in liver, which are used in brain as energetic fuel. These compounds are bioconverted by mitochondrial D-3-hydroxybutyrate dehydrogenase (BDH) E.C. 1.1.1.30. Here we report, the function and the expression of BDH in terms of catalytic activities, kinetic parameters, levels of protein and mRNA in both tissues i.e brain and liver, in relation to the hibernating process.

Results

We found that: 1/ In euthemic jerboa the specific activity in liver is 2.4- and 6.4- fold higher than in brain, respectively for AcAc reduction and for BOH oxidation. The same differences were found in the hibernation state. 2/ In euthermic jerboa, the Michaelis constants, K_M BOH and K_M NAD⁺ are different in liver and in brain while K_M AcAc, K_M NADH and the dissociation constants, K_D NAD⁺and K_D NADH are similar. 3/ During prehibernating state, as compared to euthermic state, the liver BDH activity is reduced by half, while kinetic constants are strongly increased except K_D NAD⁺. 4/ During hibernating state, BDH activity is significantly enhanced, moreover, kinetic constants (K_M and K_D) are strongly modified as compared to the euthermic state; i.e. K_D NAD⁺ in liver and K_M AcAc in brain decrease 5 and 3 times respectively, while K_D NADH in brain strongly increases up to 5.6 fold. 5/ Both protein content and mRNA level of BDH remain unchanged during the cold adaptation process.

Conclusions

These results cumulatively explained and are consistent with the existence of two BDH enzymatic forms in the liver and the brain. The apoenzyme would be subjected to differential conformational folding depending on the hibernation state. This regulation could be a result of either post-translational modifications and/or a modification of the mitochondrial membrane state, taking into account that BDH activity is phospholipid-dependent.

     

Radical copolymerization of acrylonitrile with 2,2,2‐trifluoroethyl acrylate for dielectric materials: Structure and characterization

Radical copolymerization based on acrylonitrile (AN) and 2,2,2‐Trifluoroethyl acrylate (ATRIF) initited by AIBN was investigated in acetonitrile solution. The resulting poly(AN‐co‐ATRIF) copolymers were characterized by ¹H, ¹³C, and ¹⁹F NMR and IR spectroscopy, and size exclusion chromatography (SEC). Their compositions were assessed by ¹H NMR. The kinetics of radical copolymerization of AN with ATRIF was investigated from sereval experiments achieved at 70 °C from initial [AN]₀/[ATRIF]₀ molar ratios ranging between 20/80 and 80/20 and was enabled to determine the reactivity ratios of both comonomers. From the monomer—polymer copolymerization curve, the Fineman–Ross and Kelen–Tüdos laws enabled to assess the reactivity ratios (r_AN= r₁ = 1.25 ± 0.04 and r_ATRIF = r₂ = 0.93 ± 0.05 at 70 °C) while the revised patterns scheme led to r₁₂ = r_AN = 1.03, and r₂₁ = r_ATRIF = 0.78 at 70 °C. In all cases, r_AN x r_ATRIF product was close to unity, which indicates that poly(AN‐co‐ATRIF) copolymers exhibit a random structure. This was also confirmed by the Igarashi's and Pyun's laws which revealed the presence of AN‐ATRIF, AN‐AN, and ATRIF‐ATRIF dyads. The Q and e values for ATRIF were also assessed (Q₂ = 0.62 and e₂ = 0.93). The glass transition temperature values, T_g, of these copolymers increased from 17 to 61 °C as the molar percentage of ATRIF decreased from 77 to 16% in the copolymer. Thermogravimetry analysis of poly(AN‐co‐ATRIF) copolymers showed a good thermal stability compared to that of poly(ATRIF) homopolymer due to incorporation of AN comonomer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3856–3866     

Seed coat metabolite profiling of cowpea (Vigna unguiculata L. Walp.) accessions from Ghana using UPLC-PDA-QTOF-MS and chemometrics

Abstract

Cowpea (Vigna unguiculata L. Walp.) is an important grain legume in Africa exhibiting high morpho-genetic diversity. However, not much information exists on the phytochemical profiles of its hulls. This study explored the metabolite profiles of seed-coats from thirteen cowpea accessions of varying phenotypes using UPLC-QTOF-MS and chemometric analysis. A total of 34 secondary metabolites were identified, which comprised phenolic acids, flavonoids, anthocyanins, sphingolipids and fatty acids. Quantification of selected phenolic compounds revealed marked variations among the cowpea accessions. The chemical profiles of the test accessions were distinguished by multivariate analysis, and the results revealed a marked influence of seed-coat pigmentation on the observed differences in their metabolite profiles. Moreover, delphinidin (traces to 2257.6 µg/g), catechin glucoside (traces to 2840.6 µg/g), catechin (traces to 2089.2 µg/g) and epicatechin (26.3 to 3222.7 µg/g) contributed to the segregation amongst the studied samples. The concentrations of the discriminant metabolites were greater in the dark seeded cowpeas compared to their lighter seeded counterparts. The findings represent a useful contribution to the literature on cowpea seed coat metabolites, and also reveal their potential for use in the development of food and pharmaceutical products.     

Selective Detection of Dopamine in Presence of Ascorbic Acid by Use of Glassy‐Carbon Electrode Modified with Amino‐β‐Cyclodextrin and Carbon Nanotubes

A glassy carbon electrode modified with per‐6‐amino‐β‐cyclodextrin (β‐CDNH₂) and functionalized single‐walled carbon nanotubes (SWCNT‐COOH) was elaborated. This structure was investigated for the detection of dopamine acid (DA) in presence of ascorbic acid (AA). The sensor behavior was studied by cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy. The analysis results show that the electrode modification with CD derivative improves the sensitivity and selectivity of the DA recognition; the electrochemical response was further improved by introduction of SWCNT‐COOH. The sensor shows good and reversible linear response toward DA within the concentration range of 7×10^?7–10^?4 M with a detection limit of 5×10^?7 M.     

Polyphenols contents,heavy metals analysis and in vitro antibacterial activity of extracts from Cladanthus arabicus and Bubonium imbricatum of Moroccan Origin

Abstract

Aim of this study was to evaluate polyphenols and major and trace elements of Cladanthus arabicus and Bubonium imbricatum, along with their in vitro antibacterial activity against six multidrug resistant Enterobacteriaceae (Escherichia coli S33/16, E. coli S34/16, Proteus mirabilis S32/16, Klebsiella pneumoniae S12/16, Enterobacter cloacae S5/16, and Salmonella sp S12/14). UV spectrophotometry, ultra-high-performance liquid chromatography coupled to mass spectrometry and inductively coupled plasma mass spectrometry were used to evaluate total polyphenol content, quali-quantitative profile of single polyphenols and inorganic elements of the extract. The antibacterial activity was investigated by standard methods. Twelve polyphenols were identified in both plants and these were more concentrated in B. imbricatum than C. arabicus extracts. High levels of minerals, essential trace elements and tolerable levels of heavy metals (Cd, As and Pb) were found. Furthermore, the extracts showed also a strong in vitro antibacterial activity, particularly versus E. coli S33/16 (MIC, 0.125?mg ml^?1).     

Intramolecular hydrogen bonding in structural conformers of 2‐amino methylene malonaldehyde: AIM and NBO studies

The molecular structure and intramolecular hydrogen bond energies of 44 conformers of 2‐Amino methylene malonaldehyde were investigated at MP2 and B3LYP levels of theory using the standard 6‐311++G** basis set and AIM and NBO analysis. The calculated geometrical parameters and conformational analysis in gas phase show that the closed ring via intramolecular hydrogen bonded conformers of this compound are more stable than the other ones. Hydrogen bond energies for H‐bonded conformers were obtained from the related rotamers method (RRM) and Schuster method, and also the nature of H‐bonding of them has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. Delocalization effects can be identified from the presence of off diagonal elements of the Fock matrix in the NBO basis. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Novel Copolymers of Difluoro Ring-substituted 2-Phenyl-1,1-dicyanoethylenes with 4-Fluorostyrene: Synthesis,Structure and Dielectric Study

Copolymerization of fluorine ring-substituted 2-phenyl-1,1-dicyanoethenes, RC₆H₃CH?C(CN)₂ (R is 2,3-F,F, 2,4-F,F, 2,5-F,F, 2,6-F,F, and 4-CF₃) with 4-fluorostyrene were prepared in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the copolymers were characterized by IR, ¹H and ¹³C-NMR, GPC, DSC, and TGA. The monomer reactivity ratios for 4-fluorostyrene (M₁), r₁ = 0.6 and 2-(2,4-difluorophenyl)-1,1-dicyanoethene (M₂), r₂ = 0 were determined from Fineman-Ross plot. The order of relative reactivity (1/r₁) for difluoro-substituted monomers is 2,4-F,F (0.31) > 2,3-F,F (0.25) > 2,5-F,F (0.22) > 2,6-F,F (0.10). DSC curves showed that the copolymers were amorphous with high T _g in comparison with that poly(4-fluorostyrene) indicating a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer units. From the thermogravimetric analysis, the copolymers began to degrade in the range 214–260°C. The copolymer of 4-fluorostyrene and 2-(2,4-difluorophenyl)-1,1-dicyanoethene and poly(4-fluorostyrene) were dielectrically characterized in the range 25–200°C. The dominating relaxation process detected in both materials was the α-relaxation, associated with the dynamic glass transition. The relationship polarity-permittivity was discussed.