Thiol-Ene Click Cross-linking of Starch Oleate Films for Enhanced Properties.

Biobased films were synthesized from starch oleate (DS = 2.2) cross-linked with polyethylene glycol with Mn = 2000 and 1000 g · mol-1, and ethylene glycol, all of which were esterified with either lipoic acid (LA) or 3-mercaptopropionic acid (MPA). Cross-linking was achieved through a UV-initiated thiol-ene click, and confirmed by Fourier transform infrared spectroscopy and rheometry. The films exhibit higher degradation temperatures, and an increased degree of crystallinity as cross-linker length increased. The introduction of MPA-based cross-linkers resulted in hydrophilic films, while the contact angle was barely affected by the addition of LA-based cross-linkers. A reduction in maximum strength upon introducing the cross-linkers was observed, while an increase in elongation was observed for most of the LA-based cross-linkers. Our results demonstrate the potential for tuning the mechanical and thermal properties of starch-based films through the cross-linker choice, with some formulations exhibiting increased flexibility that may be well suited for packaging applications.

Starch ester film properties: The role of the casting temperature and starch its molecular weight and amylose content.

Oleic acid and 10-undecenoic acid were used to esterify corn, tapioca, potato and a waxy potato starch, with a maximum degree of substitution of 2.4 and 1.9 respectively. The thermal and mechanical properties were investigated as a function of the amylopectin content and Mw of starch, and by the fatty acid type. All starch esters had an improved degradation temperature regardless of their botanical origin. While the Tg did increase with increasing amylopectin content and Mw, it decreased with increasing fatty acid chain length. Moreover, films with different optical appearances were obtained by varying the casting temperature. SEM and polarized light microscopy showed that films cast at 20 °C had porous open structures with internal stress, which was absent when cast at higher temperatures. Tensile test measurements revealed that films had a higher Young's modulus when containing starch with a higher Mw and amylopectin content. Besides that, starch oleate films were more ductile than starch 10-undecenoate films. In addition, all films were resistant to water at least up to one month, while some light-induced crosslinking took place. Finally, starch oleate films showed antibacterial properties against Escherichia coli, whereas native starch and starch 10-undecenoate did not.

Synthesis and Properties of Fully Biobased Crosslinked Starch Oleate Films.

Starch oleate (degree of substitution = 2.2) films were cast and crosslinked in the presence of air using UV curing (UVC) or heat curing (HC). A commercial photoinitiator (CPI, Irgacure 184) and a natural photoinitiator (NPI, a mixture of biobased 3-hydroxyflavone and n-phenylglycine) were used for UVC. No initiator was used during HC. Isothermal gravimetric analyses, Fourier Transform Infrared (FTIR) measurements, and gel content measurements revealed that all three methods were effective in crosslinking, with HC being the most efficient. All methods increased the maximum strengths of film, with HC causing the largest increase (from 4.14 to 7.37 MPa). This is consistent with a higher degree of crosslinking occurring with HC. DSC analyses showed that the Tg signal flattened as film crosslink densities increased, even disappearing in the case of HC and UVC with CPI. Thermal gravimetric analyses (TGA) indicated that films cured with NPI were least affected by degradation during curing. These results suggest that cured starch oleate films could be suitable for replacing the fossil-fuel-derived plastics currently used in mulch films or packaging applications.

A more efficient synthesis and properties of saturated and unsaturated starch esters.

This work presents a series of starch esters synthesized via 1,5,7-triazabicyclo[4.4.0]-dec-5-ene (TBD) catalyzed transesterifications in dimethyl sulfoxide (DMSO). The reaction was performed with saturated and unsaturated fatty acids (8, 11, and 18 carbon atoms). The degree of substitution (DS) was raised by purging the reaction flask with nitrogen instead of simply performing the reaction under a nitrogen atmosphere. The increase of DS was most obvious for long-chain fatty acids, as an almost complete DS was observed for starch stearate (2.8) and starch oleate (2.7). The products were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and X-ray diffraction. Starch esters from unsaturated fatty acids have a lower Tg than their saturated analogues. Moreover, contact angle and moisture uptake measurements showed increased hydrophobicity for all starch esters in comparison to pristine starch. Our results show a more efficient method for synthesizing a biobased material that steers into the direction of a material that could replace conventional plastics.

Femtosecond spectroscopic studies of the one- and two-photon excited-state dynamics of 2,2,17,17-tetramethyloctadeca-5,9,13-trien-3,7,11,15-tetrayne: a trimeric oligodiacetylene.

The excited-state dynamics of an oligomer of polydiacetylene, 2,2,17,17-tetramethyloctadeca-5,9,13-trien-3,7,11,15-tetrayne, dissolved in n-hexane have been studied by femtosecond fluorescence upconversion and polarized transient absorption experiments under one- and two-photon excitation conditions. Spectroscopically monitoring the population relaxation in the excited states in real time results in a distinct time separation of the dynamics. It has been concluded that the observed dynamics can be fully accounted for on the basis of the two lower excited states of the target molecule. The S1 (2(1)Ag) state, which cannot be excited from the ground state with one-photon absorption, is verified to be populated via internal conversion in 200+/-40 fs from the strong dipole-allowed S2 (1(1)Bu) state. The population in the "hot" S1 state subsequently cools with a time constant of 6+/-1 ps and decays back to the ground state with a lifetime of 790+/-12 ps.

Spectroscopic studies of oligodiacetylenes in solution and polymer film.

The photophysical properties of a series of monomeric, dimeric and trimeric oligodiacetylenes (ODAs; oligoenynes) bearing trimethylsilyl, t-butyl and n-octyl end-capping substituents were studied in solution and in a polymer film. Emission studies show a significant emission of oligodiacetylenes in solution, which increased with increased conjugation. This is remarkable given the near absence of fluorescence in oligoenes of similar length (e.g. hexatriene) and polydiacetylenes (PDAs), which constitute the conjugation limit. A large Stokes shift was observed, and shown to originate from an energy difference between the Franck-Condon excited state and the fluorescent state. From near-identical angles obtained for the absorption and emission dipoles it was concluded that the overall geometry of ODAs does not significantly change upon electronic transition.