Development of high bio‐content polypropylene composites with different industrial lignins

Sustainability, eco‐efficiency, pollution prevention, industrial ecology, and green chemistry are considering platform‐based approaches to the development of the next generation of products and processes. Recently, renewable alternatives to traditional petroleum‐derived plastics have motivated recent interest in bio‐based composite materials which can contribute to the reduction of the environmental footprint. Lignin is a complex and amorphous biopolymer with a high density of functional groups and high modulus, which makes it potentially promising for material applications. In this sense, lignin can potentially be employed to improve the performance of materials and an economical alternative to convert lignin into high value‐added materials. Two different types of Kraft lignin were incorporated into polypropylene to fabricate composites with high bio‐content. In this study, polypropylene, Kraft lignin, and coupling agent were subjected to reactive extrusion. The composites prepared by melt processing were compared in terms of morphological, mechanical, and thermal characterizations. The results revealed that the incorporation of lignin into polypropylene matrix resulted in composites with properties suitable for various industrial sectors, especially those in which mechanical and thermal properties are crucial, such as the replacement of engineering plastics and polypropylene mineral filled. As a result, this work provides an effective way of using lignin as a low‐cost bio‐renewable resource in the plastics industry.     

Elucidating Solvent Effects on Strong Intramolecular Hydrogen Bond: DFT-MD Study of Dibenzoylmethane in Methanol Solution

The dynamic aspect of solvation plays a crucial role in determining properties of strong intramolecular hydrogen bonds since solvent fluctuations modify instantaneous hydrogen-bonded proton transfer barriers. Previous studies pointed out that solvent-solute interactions in the first solvation shell govern the position of the proton but the ability of the electric field due to other solvent molecules to localize the proton remains an important issue. In this work, we examine the structure of the O−H⋅⋅⋅O intramolecular hydrogen bond of dibenzoylmethane in methanol solution by employing density functional theory-based molecular dynamics and quantum chemical calculations. Our computations showed that homogeneous electric fields with intensities corresponding to those found in polar solvents are able to considerably alter the proton transfer barrier height in the gas phase. In methanol solution, the proton position is correlated with the difference in electrostatic potentials on the oxygen atoms of dibenzoylmethane even when dibenzoylmethane-methanol hydrogen bonding is lacking. On a timescale of our simulation, the hydrogen bonding and solvent electrostatics tend to localize the proton on different oxygen atoms. These findings provide an insight into the importance of the solvent electric field on the structure of a strong intramolecular hydrogen bond.     

Inclusion Complexes of Cyclodextrins with 4-Amino-1,8-Naphthalimides

The formation of inclusion complexes between 4-amino-1,8-naphthalimides and cyclodextrins (CDs) was investigated. The naphthalimides used in the study were 4-amino-1,8-naphthalimide (I) and4-(2-phosphonoethylamino)-N-(2-phosphonoethyl)-1,8-naphthalimide,tetraethylester (II). The CDs employed were -CD, -CD, -CD, HP--CD, HP--CD andHP--CD (HP = hydroxypropyl). Evidence for complex formation was obtained from the changes in the fluorescence spectra of the dyes in the presence of increasing amounts of the CDs. The most striking changes were observed with HP--CD and HP--CD. Treatment of the data using Benesi–Hildebrand plotswas consistent with a 1:1 inclusion model. The determined stabilityconstants were (K_eq, M^-1): 106 (I:HP--CD, pH = 2.0), 193 (I:HP--CD, pH = 7.0), 113 (I:HP--CD, pH = 7.0), 155(II:HP--CD, pH = 2.0), 121 (II:HP--CD,pH = 7.0), 301 (II:HP--CD, pH = 7.0). It can beconcluded that compound I forms a more stable complex with HP--CD than with HP--CD. Compound II, on the other hand, forms a more stable complex with HP--CD than with HP--CD.     

Pentavalent organoantimonial derivatives: two simple and efficient synthetic methods for meglumine antimonate

Two simple and efficient procedures for the preparation of pentavalent antimony derivatives are described, using either antimony pentachloride (SbCl₅) or potassium hexahydroxoantimonate (KSb(OH)₆) as sources of antimony(V). These two new methods are evaluated for the synthesis of an important anti‐leishmanial drug: meglumine antimonate. Using elemental (carbon, hydrogen, nitrogen) and thermal analysis, atomic absorption (antimony), proton NMR spectroscopy and high‐resolution positive‐ion electrospray ionization mass spectrometry (ESI(+)‐MS), products for the reaction with N‐methyl‐D ‐glucamine (NMG) using both the SbCl₅ and KSb(OH)₆ methods were characterized and found to be similar to a commercial sample of the drug. The only notable difference was observed for the ESI‐MS spectrum of the KSb(OH)₆ product; it displays the same pattern of ESI‐generated ions as those of both the SbCl₅ product and the commercial drug, but with significantly different abundance ratios. NMR data indicate that the NMG molecules coordinate antimony in two different fashions, which suggests either the coexistence of two different complexes or the existence of a single major complex in which two NMG molecules are coordinated with antimony in an asymmetrical geometry. Copyright © 2003 John Wiley & Sons, Ltd.     

Wittig reaction with partially protected sugar lactol derivatives. Preparation of highly cytotoxic goniofufurone analogues

A new approach to the dephenyl goniofufurone analogue 2 and the corresponding (3S,4R)-stereoisomer 3 is reported. The resulting furanolactones 2 and 3 have shown a potent and selective in vitro cytotoxicity against certain human tumour cell lines.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

Perturbation of wavelet and Gabor frames

In this work two aspects of theory of frames are presented: a side necessary condition on irregular wavelet frames is obtained, another perturbation of wavelet and Gabor frames is considered. Specifically,we present the results obtained on frame stability when one disturbs the mother of wavelet frame, or the parameter of dilatation, and in Gabor frames when the generating function or the parameter of translation are perturbed. In all cases we work without demanding compactness of the support, neither on the generating function, nor on its Fourier transform.     

Structure of the Semi-Classical Amplitude for General Scattering Relations

ABSTRACT

We consider scattering by general compactly supported semi-classical perturbations of the Euclidean Laplace-Beltrami operator. We show that if the suitably cut-off resolvent quantizes a Lagrangian relation on the product cotangent bundle, the scattering amplitude quantizes the natural scattering relation. In the case when the resolvent is tempered, which is true at non-trapping energies or at trapping energies under some non-resonance assumptions, and when we work microlocally near a non-trapped ray, our result implies that the scattering amplitude defines a semiclassical Fourier integral operator associated to the scattering relation in a neighborhood of that ray. Compared to previous work, we allow this relation to have more general geometric structure.