Cellulose microfibrils from banana farming residues: isolation and characterization

Cellulose microfibrils have been prepared from banana rachis using a combination of chemical and mechanical treatments. The morphology and structure of the samples were characterized using transmission electron microscopy, atomic force microscopy, and X-ray diffraction. Fourier-transformed infrared spectroscopy (FTIR) was used to characterize the chemical modifications of the samples after each treatment. Suspensions of bundled or individualized 5-nm-wide microfibrils were obtained after homogenization (PH) whereas an organosolv (PO) treatment resulted in shorter aggregates of parallel cellulose microcrystallites. The sharper rings in the X-ray diffraction pattern of the PO-treated sample suggest a higher crystallinity due to a more efficient removal of hemicelluloses and dissolution of amorphous zones by the acid treatment. Both microfibrils and microcrystals prepared by both methods can be used as reinforcing filler in nanocomposite materials.     

Bis[bis-(4-alkoxyphenyl)amino] derivatives of dithienylethene, bithiophene, dithienothiophene and dithienopyrrole: palladium-catalysed synthesis and highly delocalised radical cations

Five diamines with thiophene-based bridges--(E)-1,2-bis{5-[bis(4-butoxyphenyl)amino]-2-thienyl}ethylene (1), 5,5'-bis[bis(4-methoxyphenyl)amino]-2,2'-bithiophene (2), 2,6-bis[bis(4-butoxyphenyl)amino]dithieno[3,2-b:2',3'-d]thiophene (3), N-(4-tert-butylphenyl)-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 a) and N-tert-butyl-2,6-bis[bis(4-methoxyphenyl)amino]dithieno[3,2-b:2',3'-d]pyrrole (4 b)--have been synthesised. The syntheses make use of the palladium(0)-catalysed coupling of brominated thiophene species with diarylamines, in some cases accelerated by microwave irradiation. The molecules all undergo facile oxidation, 4 b being the most readily oxidised at about -0.4 V versus ferrocenium/ferrocene, and solutions of the corresponding radical cations were generated by addition of tris(4-bromophenyl)aminium hexachloroantimonate to the neutral species. The near-IR spectra of the radical cations show absorptions characteristic of symmetrical delocalised species (that is, class III mixed-valence species); analysis of these absorptions in the framework of Hush theory indicates strong coupling between the two amine redox centres, stronger than that observed in species with phenylene-based bridging groups of comparable length. The strong coupling can be attributed to high-lying orbitals of the thiophene-based bridging units. ESR spectroscopy indicates that the coupling constant to the amino nitrogen atoms is somewhat reduced relative to that in a stilbene-bridged analogue. The neutral species and the corresponding radical cations have been studied with the aid of density functional theory and time-dependent density functional theory. The DFT-calculated ESR parameters are in good agreement with experiment, while calculated spin densities suggest increased bridge character to the oxidation in these species relative to that in comparable species with phenylene-based bridges.     

Vibronic coupling in organic semiconductors: the case of fused polycyclic benzene-thiophene structures

The nature of vibronic coupling in fused polycyclic benzene-thiophene structures has been studied using an approach that combines high-resolution gas-phase photoelectron spectroscopy measurements with first-principles quantum-mechanical calculations. The results indicate that in general the electron-vibrational coupling is stronger than the hole-vibrational coupling. In acenedithiophenes, the main contributions to the hole-vibrational coupling arise from medium- and high-frequency vibrations. In thienobisbenzothiophenes, however, the interaction of holes with low-frequency vibrations becomes significant and is larger than the corresponding electron-vibrational interaction. This finding is in striking contrast with the characteristic pattern in oligoacenes and acenedithiophenes in which the low-frequency vibrations contribute substantially only to the electron-vibrational coupling. The impact of isomerism has been studied as well.     

Novel RPLC stationary phases for lipophilicity measurement: solvatochromic analysis of retention mechanisms for neutral and basic compounds

An RPLC was developed to rapidly determine lipophilicity of neutral and basic compounds using three base deactivated RPLC stationary phases particularly designed for the analysis of basic compounds, namely, Supelcosil ABZ(+)Plus, Discovery RP Amide C16, and Zorbax Extend C18. The work consisted of three sets of experiments. In the first log kw values of neutral compounds were extrapolated using hydroorganic mobile phases at different compositions. Good correlation between log kw and log Poct indicated that the method was appropriate for these supports, without adding a silanol masking agent. In the second set of experiments, isocratic log k values of neutral and basic compounds were measured with three different mobile phases. The best estimation of lipophilicity was obtained for neutral and basic compounds when the secondary interactions were strongly reduced (i. e., when basic compounds were under their neutral form). In the third set of experiments, isocratic retention factors of basic compounds (in their neutral form) were measured with a high-pH mobile phase, on a chemically stable support (Zorbax Extend C18). Under these chromatographic conditions, correlation between the isocratic retention factors and log Poct (log D10.5) for basic compounds was similar to that for neutral compounds.     

Influence of plasticizers and crosslinking on the properties of biodegradable films made from sodium caseinate

Plasticized protein films were prepared by the casting method from water solution of sodium caseinate and plasticizers with the aim to obtain environmentally friendly materials for packaging applications. Mechanical properties (tensile strength, elongation and Young’s modulus) of caseinate based films were determined versus ratio of protein to plasticizer, plasticizer type and relative humidity conditions. Among the different polyol-type plasticizers tested, glycerol (Gly) and triethanolamine (TEA) were the most efficient for the improvement of mechanical properties (high strains for low stresses). Further, chemical crosslinking between formaldehyde (HCHO) and free amino groups (ε-NH₂) of sodium caseinate was performed to increase water resistance of TEA plasticized films. Optimal mechanical properties, i.e. elastic modulus of 105 MPa, tensile strength of 8-9 MPa for elongation at break about 110-125% were obtained for HCHO/ε-NH₂ ratios higher than 1.35. Protein specific water solubility was determined from a 280 nm absorbance. For convenient crosslinker (HCHO) content sodium caseinate solubility can be lowered to less than 5 wt% after 24 h immersion in water.     

Design of pi-conjugated organic materials for one-dimensional energy transport in nanochannels

Various end-substituted distyrylbenzenes have been synthesized to serve as guest molecules in inclusion compounds to promote efficient energy transport along one-dimensional channels. Their optical and photophysical properties have been characterized at both experimental and theoretical levels. All molecules display a large transition dipole moment between the ground state and lowest excited state and hence a short radiative lifetime (on the order of 1-2 ns). They also exhibit a large spectral overlap between the emission and absorption spectra, which enables efficient energy transport between molecules arranged in a head-to-tail configuration in nanochannels. Hopping rates on the order of 10(12) s(-1) are calculated at a full quantum-chemical level; this is much larger than the radiative lifetimes and opens the way for energy migration over large distances. Changes in the nature of the terminal substituents are found to modulate the optical properties weakly but to impact significantly the energy transfer rates.     

Morphology and Structure of Crystalline Polysaccharides: Some Recent Studies

Summary: In this paper, we review recent studies on the morphology and molecular structure of some polysaccharide crystals from amylose, cellulose, and mannan. The data were recorded using combinations of imaging, diffraction, and spectroscopic techniques: scanning and transmission electron microscopy, electron, neutron, and X-ray diffraction, as well as ¹³C solid-state NMR spectroscopy. Differences were generally found between native crystals, whose features result from in vivo biogenesis and the recrystallized products prepared in vitro.     

Rapid stereoselective separations of amphetamine derivatives with highly sulfated gamma-cyclodextrin

The highly sulfated gamma-CD (HS-gamma-CD) is a chiral selector widely used in CE for the enantioseparation of pharmaceutical compounds. This paper investigated different approaches to reduce the stereoselective analysis time of amphetamine (AT) derivatives according to the chiral selector concentration in the BGE. With high HS-gamma-CD concentration, tested analytes were separated in 3.5 min as anionic complexes with short-end injection technique in reversed polarity mode. However, this procedure presented some limitations in terms of efficiency and resolution, excessive Joule heating and poor compatibility with MS detection. With low HS-gamma-CD concentration, compounds were separated as cations. Conventional approaches to reduce CE analysis time demonstrated critical resolution between some analytes. Therefore, the use of the partial-filling technique compatible with MS detection was carried out. Under optimized conditions, the analysis time for the chiral separation of seven AT like compounds was reduced to 6 min. Moreover, sensitivity of CE-MS was sufficient for the determination of ATs in plasma following a simple liquid-liquid extraction.     

Measurement of Total and Unbound Mycophenolic Acid and Its Glucuronide by LC Coupled with MS. Application to a Pharmacokinetic Study of Mycophenolate Mofetil in Patients with Autoimmune Diseases

Liquid chromatography coupled with mass spectrometry for the determination of total and unbound mycophenolic acid and its major metabolite in human plasma has been developed. Sample preparations were based on a fully automated solid-phase extraction process and ultrafiltration. Mass spectrometric data were acquired in a single-ion monitoring method. The analytes and nevirapine (internal standard) were well separated in an isocratic mode over 8 min. Validation study exhibited excellent linearity, with intra- and inter-day precision and accuracy of less than 12%. The assay was successfully applied to the pharmacokinetic study of mycophenolic acid in patients with autoimmune diseases.     

Optimizing the source distribution in fluid mixing

A passive scalar is advected by a velocity field, with a nonuniform spatial source that maintains concentration inhomogeneities. For example, the scalar could be temperature with a source consisting of hot and cold spots, such that the mean temperature is constant. Which source distributions are best mixed by this velocity field? This question has a straightforward yet rich answer that is relevant to real mixing problems. We use a multiscale measure of steady-state enhancement to mixing and optimize it by a variational approach. We then solve the resulting Euler-Lagrange equation for a perturbed uniform flow and for simple cellular flows. The optimal source distributions have many broad features that are as expected: they avoid stagnation points, favour regions of fast flow, and their contours are aligned such that the flow blows hot spots onto cold and vice versa. However, the detailed structure varies widely with diffusivity and other problem parameters. Though these are model problems, the optimization procedure is simple enough to be adapted to more complex situations.