Bioconversion Process of Polyethylene from Waste Tetra Pak® Packaging to Polyhydroxyalkanoates.

Presented herein are the results of a novel recycling method for waste Tetra Pak® packaging materials. The polyethylene (PE-T) component of this packaging material, obtained via a separation process using a "solvents method", was used as a carbon source for the biosynthesis of polyhydroxyalkanoates (PHAs) by the bacterial strain Cupriavidus necator H16. Bacteria were grown for 48-72 h, at 30 °C, in TSB (nitrogen-rich) or BSM (nitrogen-limited) media supplemented with PE-T. Growth was monitored by viable counting. It was demonstrated that C. necator utilised PE-T in both growth media, but was only able to accumulate 40% w/w PHA in TSB supplemented with PE-T. Only 1.5% w/w PHA was accumulated in the TSB control, and no PHA was detected in the BSM control. Extracted biopolymers were characterised by nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) spectroscopy, electrospray tandem mass spectrometry (ESI-MS/MS), gel permeation chromatography (GPC), and accelerator mass spectrometry (AMS). The characterisation of PHA by ESI-MS/MS revealed that PHA produced by C. necator in TSB supplemented with PE-T contained 3-hydroxybutyrate, 3-hydroxyvalerate, and 3-hydroxyhexanoate co-monomeric units. AMS analysis also confirmed the presence of 96.73% modern carbon and 3.27% old carbon in PHA derived from Tetra Pak®. Thus, this study demonstrates the feasibility of our proposed recycling method for waste Tetra Pak® packaging materials, alongside its potential for producing value-added PHA, and the ability of 14C analysis in validating this bioconversion process.

Oxidized Polyethylene Wax as a Potential Carbon Source for PHA Production.

We report on the ability of bacteria to produce biodegradable polyhydroxyalkanoates (PHA) using oxidized polyethylene wax (O-PEW) as a novel carbon source. The O-PEW was obtained in a process that used air or oxygen as an oxidizing agent. R. eutropha H16 was grown for 48 h in either tryptone soya broth (TSB) or basal salts medium (BSM) supplemented with O-PEW and monitored by viable counting. Study revealed that biomass and PHA production was higher in TSB supplemented with O-PEW compared with TSB only. The biopolymers obtained were preliminary characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The detailed structural evaluation at the molecular level was performed by electrospray ionization tandem mass spectrometry (ESI-MS/MS). The study revealed that, when TSB was supplemented with O-PEW, bacteria produced PHA which contained 3-hydroxybutyrate and up to 3 mol % of 3-hydroxyvalerate and 3-hydroxyhexanoate co-monomeric units. The ESI-MS/MS enabled the PHA characterization when the content of 3-hydroxybutyrate was high and the appearance of other PHA repeating units was very low.

A new efficient method for the processing of post-consumer polypropylene and other polyolefin wastes into polar waxes.

This paper describes a new efficient method for the processing of post-consumer polypropylene (and other polyolefins) wastes into polar waxes that have potential applications. This technology includes two key steps. In the first step, the post-consumer polyolefins are purified mostly from oil which is used as a solvent in processing of polyolefin wastes (like metalized polyolefin films), and in the second step, the oxidative degradation process is initiated to obtain polar waxes or, alternatively, the purified polymer can be granulated. The results of laboratory research on both steps are presented, as well as a comparison of the obtained granulates and polar waxes with commercially available products.

Inverse gas chromatography investigation of oxidized polyolefins: surface properties.

Oxidized polyolefins were obtained in processes with the use of air or oxygen as oxidizing agent. The oxidation process caused partial polymer degradation and the change of the surface properties of examined materials. The magnitude of these changes was estimated by means of inverse gas chromatography. All oxidized materials were found to exhibit slightly acidic character. Surface properties strongly depend on the content of oxygen functional groups (oxidation degree) and type of initial material. The most active surfaces were found for oxidized polypropylene and polyethylene wax. The use of principal component analysis allowed to select four parameters offering complete information on the physiochemical character of examined materials (γS(D)), acid volume or saponification number, KA or KD and KA/KD.

Correlation of substituted aromatic ß-diketones' characteristic protons chemical shifts with Hammett substituent constants.

Influence of dibenzoylmethane's substituents in meta and para positions on chemical shift values of tautomers' characteristic protons was investigated in four solvents with (1)H NMR spectroscopy: acetone-d(6), benzene-d(6), CDCl(3) and deuterated dimethyl sulfoxide (DMSO-d(6)). It was proved that the influence of substituents on chemical shifts strongly depends on the kind of the solvent; the greatest changes were observed in benzene-d6 and the smallest in CDCl(3). In acetone-d(6) and DMSO-d(6), the influence of substituents on chemical shifts is similar and the most regular. It allowed a fair correlation of chemical shifts of para-substituted dibenzoylmethane derivatives' characteristic protons with Hammett substituent constants in these solvents. In CDCl(3), characteristic protons' chemical shifts were near (1)H NMR spectroscopy measurement error limits, and, therefore, correlation with Hammett substituent constants in this solvent was unsatisfactory. In benzene, although the changes of chemical shifts are the most evident, the changes are also the most irregular, and, therefore, correlation in this solvent failed completely. Results of meta-substituted derivatives were much more irregular, and their correlation with Hammett substituent constants was poor in all investigated solvents.

Influence of substituent on UV absorption and keto-enol tautomerism equilibrium of dibenzoylmethane derivatives.

UV absorption spectra of dibenzoylmethane and its 23 derivatives with acetamide, tert-butyl, chloride, fluoride, hydroxyl, methyl, methoxy and nitro substituents in aromatic rings were collected. General influence of substituent on absorption maxima and absorption intensity was defined. Hyperchromic effects were observed for diketones with electron-donating groups in para postion. The keto-enol tautomerism equilibrium constant of obtained compounds was investigated with (1)H NMR spectroscopy. Significant changes of equilibrium were observed only for ortho substituted compounds. Results revealed dissimilarity of substituent effects on absorption and keto-enol tautomerism of aromatic ß-diketones.

UV absorption and keto-enol tautomerism equilibrium of methoxy and dimethoxy 1,3-diphenylpropane-1,3-diones.

UV absorption spectra of 1,3-diphenylpropane-1,3-dione (1), its three methoxy derivatives (2-4) and its six dimethoxy derivatives (5-10) in various solvents dissolved were collected. The keto-enol tautomerism equilibrium constant was calculated with (1)H NMR. The position of the methoxy group in 1,3-diphenylpropane-1,3-dione was shown to have an influence on the molecule's UV absorption spectrum and the keto-enol tautomerism equilibrium constant. The methoxy group in the para position increases the absorption of radiation in the UV-A range. A shift to the keto form in the keto-enol tautomerism equilibrium is experienced by compounds with methoxy groups in ortho position. When two methoxy groups are present, the influence of their position is cumulative.

1,4-Bis[(1-methyl-1-phenylethyl)peroxymethyl]benzene.

The title compound, C(26)H(30)O(4), is one of the first alkyl bis-peroxides to be structurally characterized. The molecule lies on a centre of inversion and therefore the terminal phenyl rings are parallel. Although there are three aromatic rings in the molecule, the C-O-O-C torsion angle of 163.10 (10) degrees is close to the value found in Me(3)COOCMe(3).