Synthesis and NMR characterization of aliphatic-aromatic copolyesters by reaction of poly(ethylene terephthalate) post-consumer and poly(ethylene adipate)

An aliphatic-aromatic copolyester of poly(ethylene terephthalate), PET, and poly(ethylene adipate), PEA, PET-co-PEA, was synthesized by the high temperature melt reaction of post-consumer PET and PEA. As observed by NMR spectroscopy, the reaction yielded random copolyesters in a few minutes through ester-interchange reactions, even without added catalyst. The copolyesters obtained in the presence of a catalyst presented higher intrinsic viscosity than that obtained without the addition of catalyst, due to simultaneous polycondensation and ester-interchange reactions. The structure of the aliphatic-aromatic copolyesters obtained in different PET/PEA ratio is random as observed by NMR analysis.

Synthesis and biological activity of n-{5-(4-methylphenyl) diazenyl-4-phenyl-1, 3-thiazol-2-yl}benzamide derivatives

In the present study, various amides of 2-amino-5-(4-methylphenyl)-diazenyl-4-phenyl-1, 3-thiazole was synthesized and their biological activities were evaluated. All the synthesized compounds were characterized by the combination of elemental analysis and standard spectroscopic methods. They are screened for anti-bacterial activity against Escherichia coli and Staphylococcus aureus as well as screened for antifungal activity against Aspergillus niger and Apergillus oryzae by cup plate method at 1 µg/ mL concentration in DMF.

Synthesis and antifungal activity of halogenated aromatic bis-γ-lactones analogous to avenaciolide

Here we describe the total syntheses and characterization by elemental analyses, infrared and NMR spectroscopy of three new compounds analogous to avenaciolide, a bis-γ-lactone isolated from Aspergillus avenaceus that possesses antifungal activity, where the octyl group of the natural product was replaced by aromatic groups containing chlorine and fluorine atoms. The effects of the avenaciolide, the novel compounds and their synthetic precursors on mycelia development and conidia germination of Colletotrichum gloeosporioides and Fusarium solani were evaluated in vitro. The title compounds were almost as active as avenaciolide. The absolute structures of the chlorinated analogs were determined by X-ray diffraction analysis.

Hydrogels of cellulose acetate crosslinked with pyromellitic dianhydride: part I: synthesis and swelling kinetics

This work describes the synthesis of hydrogels of cellulose acetate (AC) crosslinked with 1,2,4,5-benzenotetracarboxylic dianhydride (PMDA). The crosslinking reaction was monitored by FTIR. Analysis of aromatic fragments from the alkaline hydrolysis of the gels by UV spectroscopy indicated that an increase in the stoichiometric ratio of dianhydride resulted in higher degrees of crosslinking. The non-porous nature of the gels was confirmed by analysis of nitrogen adsorption. Water absorption isotherms showed that as the temperature and degree of crosslinking increased, the percentage of water absorbed at equilibrium (%Seq) also increased. The hydrogels presented second order swelling kinetics.

Nanoporous materials: pillared clays and regular silicas as an example of synthesis and their porosity characterization by X-ray diffraction

Because of their practical applications, porous materials attract the attention of undergraduate students in a way that can be used to teach techniques and concepts in various chemistry disciplines. Porous materials are studied in various chemistry disciplines, including inorganic, organic, and physical chemistry. In this work, the syntheses of a microporous material and a mesoporous material are presented. The porosity of the synthesized materials is characterized by X-ray diffraction analysis. We show that this technique can be used to determine the pore dimensions of the synthesized materials.

Ultrafiltration membranes from waste polyethylene terephthalate and additives: synthesis and characterization

The synthesis and characterization of asymmetric ultrafiltration membranes from recycled polyethylene terephthalate (PET) and polyvinylpyrrolidone (PVP) is reported. PET is currently used in many applications, including the manufacture of bottles and tableware. Monomer extraction from waste PET is expensive, and this process has not yet been successfully demonstrated on a viable scale. Hence, any method to recycle or regenerate PET once it has been used is of significant importance from scientific and environmental research viewpoints. Such a process would be a green alternative due to reduced raw monomer consumption and the additional benefit of reduced manufacturing costs. The membranes described here were prepared by a phase-inversion process, which involved casting a solution containing PET, m-cresol as solvent, and polyethylene glycol (PEG) of different molecular weights as additives. The membranes were characterized in terms of pure water permeability (PWP), molecular weight cut-off (MWCO), and flux and membrane morphology. The results show that the addition of PEG with high molecular weights leads to membranes with higher PWP. The presence of additives affects surface roughness and membrane morphology.

Synthesis and thermal studies of solid state 2-chloro-benzylidenepyruvic acid and its compounds with sodium, aluminium (III), gallium (III) and indium (III) cations

The synthesis of sodium 2-chlorobenzylidenepyruvate and its corresponding acid as well as binary, binary together with it's acid or hydroxo-2-chorobenzylidenepyruvate of aluminium (III), gallium (III) and indium (III), were isolated. Chemical analysis, thermogravimetry, derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and X-ray powder diffractometry have been employed to characterize and to study the thermal behaviour of these compounds. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition.

Synthesis and characterization of solid 2-methoxycinnamylidenepyruvic acid

The 2-methoxycinnamylidenepyruvic acid (2-MeO-HCP) was synthesized and characterized for nuclear magnetic resonance (¹H and 13C NMR), mass spectrometry (MS), Infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The application of DSC for purity determination is well documented in literature and is used in the analysis of pure organic compounds. The molecular geometry and vibrational frequencies of 2-MeO-HCP have been calculated.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Pure and Fe(III)-doped TiO2 suspensions were prepared by the sol gel method with the use of titanium isopropoxide (Ti(OPri)4) as precursor material. The properties of doped materials were compared to TiO2 properties based on the characterization by thermal analysis (TG-DTA and DSC), X-ray powder diffractometry and spectroscopy measurements (FTIR). Both undoped and doped TiO2 suspensions were used to coat metallic substrate as a mean to make thin-film electrodes. Thermal treatment of the precursors at 400ºC for 2 h in air resulted in the formation of nanocrystalline anatase TiO2. The thin-film electrodes were tested with respect to their photocatalytic performance for degradation of a textile dye in aqueous solution. The plain TiO2 remains as the best catalyst at the conditions used in this report.

Synthesis and characterization of nanoperforated metal oxide thin films

For advanced devices in the application fields of data storage, solar cell and biosensing, one of the major challenges to achieve high efficiency is the fabrication of nanopatterned metal oxide surfaces. Such surfaces often require both precise structure at the nanometer scale and controllable patterned structure at the macro scale. Nowadays, the dominating candidates to fabricate nanopatterned surfaces are the lithographic technique and block-copolymer masks, most of which are unfortunately costly and inefficient. An alternative bottom-up approach, which involves organic/inorganic self-assembly and dip-coating deposition, has been studied intensively in recent years and has proven to be an effective technique for the fabrication of nanoperforated metal oxide thin films. The overall objective of this work was to optimize the synthesis conditions of nanoperforated TiO2 (NP-TiO2) thin films, especially to be compatible with mixed metal oxide systems. Another goal was to develop fabrication and processing of NP-TiO2 thin films towards largescale production and seek new applications for solar cells and biosensing. Besides the traditional dip-coating and drop-casting methods, inkjet printing was used to prepare thin films of metal oxides, with the advantage of depositing the ink onto target areas, further enabling cost-effective fabrication of micro-patterned nanoperforated metal oxide thin films. The films were characterized by water contact angle determination, Atomic Force Microscopy, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Grazing Incidence XRay Diffraction. In this study, well-ordered zinc titanate nanoperforated thin films with different Zn/Ti ratios were produced successfully with zinc precursor content up to 50 mol%, and the dominating phase was Zn2Ti3O8. NP-TiO2 structures were also obtained by a cost-efficient means, namely inkjet printing, at both ambient temperature and 60 °C. To further explore new biosensing applications of nanoperforated oxide thin films, inkjet printing was used for the fabrication of both continuous and patterned polymeric films onto NP-TiO2 and perfluorinated phosphate functionalized NP-TiO2 substrates, respectively. The NP-TiO2 films can be also functionalized with a fluoroalkylsilane, resulting in hydrophobic surfaces on both titania and silica. The surface energy contrast in the nanoperforations can be tuned by irradiating the films with UV light, which provides ideal model systems for wettability studies.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Synthesis and spectral studies of methyl heterocylic systems

2-Carboxy-2?-methyldiphenyl sulfide was prepared by the Ullmann reaction and cyclodehydrated by sulfuric acid to afford 4-methylthioxanthone. 1-Methylthioxanthone was separated from the reaction mixture obtained upon cyclodehydration of 2-carboxy-3f-methyldiphenyl sulfide. In addition, 1-, 2-, 3- and 4-methylthioxanthone 10,10-dioxides were synthesized by oxidation of the corresponding thioxanthones. o-, m- and p-N-Tolylanthranilic acids were prepared by the Ullmann reaction and used as precursors for the preparation of 1-, 2- and 4- methyl-9-chloroacridine and finally 1-, 2-, 3- and 4-methylacridone. High resolution, 60 MHz PMR spectra were obtained on the four monomethyl isomers of xanthone, thioxanthone, thioxanthone 10,10-dioxide and acridone, and on 1-, 2- and 4-methyl-9-chloroacridine. For some compounds, coupling of all three different aromatic protons to the methyl was observed, two of the couplings typically being smaller than the third. With the large (ortho) coupling being on the order of 0.5 to 1.0 Hz, it was necessary to decouple the aromatic part of the spectrum. The magnitude of the ortho benzylic constant may be related to an incomplete Tr-bond delocalization in the molecules.

Novel approaches to the synthesis and treatment of cathode materials for lithium-ion batteries

Nous avons mis au point une approche novatrice pour la synthèse d’un matériau de cathode pour les piles lithium-ion basée sur la décomposition thermique de l’urée. Les hydroxydes de métal mixte (NixMnxCo(1-2x)(OH)2) ont été préparés (x = 0.00 à 0.50) et subséquemment utilisés comme précurseurs à la préparation de l’oxyde de métal mixte (LiNixMnxCo(1-2x)O2). Ces matériaux, ainsi que le phosphate de fer lithié (LiFePO4), sont pressentis comme matériaux de cathode commerciaux pour la prochaine génération de piles lithium-ion. Nous avons également développé un nouveau traitement post-synthèse afin d’améliorer la morphologie des hydroxydes. L’originalité de l’approche basée sur la décomposition thermique de l’urée réside dans l’utilisation inédite des hydroxydes comme précurseurs à la préparation d’oxydes de lithium mixtes par l’intermédiaire d’une technique de précipitation uniforme. De plus, nous proposons de nouvelles techniques de traitement s’adressant aux méthodes de synthèses traditionnelles. Les résultats obtenus par ces deux méthodes sont résumés dans deux articles soumis à des revues scientifiques. Tous les matériaux produits lors de cette recherche ont été analysés par diffraction des rayons X (DRX), microscope électronique à balayage (MEB), analyse thermique gravimétrique (ATG) et ont été caractérisés électrochimiquement. La performance électrochimique (nombre de cycles vs capacité) des matériaux de cathode a été conduite en mode galvanostatique.

Synthesis and Characterization Of Some Transition Metal Complexes Of Multidentate Ligands

Coordination chemistry of schiff bases is of considerable interest due to their various magnetic, catalytic and biological applications. Here it describes the spectral characterization of schiff bases and its Mn (II), Cu (II) and Ni (II) complexes. Then synthesis and spectral characterization of Zn (II), Cd (II) and Co (II) complexes of schiff base derived from 3-Formylsalicilic Acid and 1,3-diaminopropane. Then it discusses the synthesis and spectral studies of Copper (II) complexes of 2-Hydroxyacetophenone N-phenyl semicarbazone. Finally it discusses the synthesis and spectral characterization of Co (III) complexes of salicylaldehyde N-phenyl semicarbazone. The preparation and characterization of Cobalt (III) complexes of salicylaldehyde, N-phenylthiosemicarbazone containing hetrocyclic bases phenalthroline and bipyridine. Thiocyanate, azide and perchlorate ions act as coligands. Elemental analysis suggests +3 state for Cobalt. HNMR, IR and UV-visible spectra characterize the complexes.

Synthesis and Characterization of Chlorinated Paraffin Wax-Bound Paraphenylenediamine Antioxidant and ItsApplication in Natural Rubber

ABSTRACT: p-Phenylenediamine was chemically attached to low molecular weight chlorinated paraffin wax. The polymer-bound p-phenylenediamine was characterized by vapor-phase osmometry (VPO), proton magnetic resonance spectroscopy ('H-NMR), infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The efficiency and permanence of the polymer-bound p-phenylenediamine as an antioxidant was compared with a conventional amine-type antioxidant in natural rubber vulcanizates. The vulcanizates showed improved aging resistance in comparison to vulcanizates containing a conventional antioxidant. The presence of liquid polymer-bound p-phenylenediamine also reduces the amount of the plasticizer required for compounding.