Photoinduced thiol–ene crosslinking of globalide/ε‐caprolactone copolymers: Curing performance and resulting thermoset properties

The increasing demand for bioderived polymers led us to investigate the potential use of the macrolactone globalide in thermoset synthesis via the photoinduced thiol–ene reaction. A series of six lipase‐catalyzed poly(globalide‐caprolactone) copolyesters bearing internal main‐chain unsaturations ranging from 10 to 50 and 100 mol % were successfully crosslinked in the melt with equal amounts of thiol groups from trimethylolpropane‐trimercapto propionate affording fully transparent amorphous elastomeric materials with different thermal and viscoelastic properties. Three major conclusions can be drawn from this study: (i) high thiol–ene conversions (>80%) were easily attained for all cases, while maintaining the cure behavior, and irrespective of functionality at reasonable reaction rates; (ii) parallel chain‐growth homopropagation of the ene monomer is insignificant when compared with the main thiol–ene coupling route; and (iii) high ene‐density copolymers result in much lower extracted sol fractions and high T_g values as a result of a more dense and homogeneous crosslinked network. The thiol–ene system evaluated in this contribution serve as model example for the sustainable use of naturally occurring 1,2‐disubstituted alkenes in making semisynthetic polymeric materials in high conversions with a range of properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Nucleoside-assisted self-assembly of oligo(p-phenylenevinylene)s at liquid/solid interface: chirality and nanostructures

The formation of DNA nucleoside-assisted π-conjugated nanostructures was studied by means of scanning tunneling microscopy (STM) and force field simulations. Upon adsorption of the achiral oligo(p-phenylenevinylene) (OPV) derivative at the liquid/solid interface, racemic conglomerates with mirror related rosettes are formed. Addition of the DNA nucleosides D- and L-thymidine, which act as "chiral handles", has a major effect on the supramolecular structure and the expression of chirality of the achiral OPV molecules. The influence of these "chiral handles" on the expression of chirality is probed at two levels: monolayer symmetry and monolayer orientation with respect to the substrate. This was further explored by tuning the molar ratio of the building blocks. Molecular modeling simulations give an atomistic insight into the monolayer construction, as well as the energetics governing the assembly. Thymidine is able to direct the chirality and the pattern of OPV molecules on the surface, creating chiral lamellae of π-conjugated dimers.     

Peptide release upon photoconversion of 2-nitrobenzyl compounds into nitroso derivatives

The photoinduced conversion via the aci-nitro into the nitroso form was studied for 4,5-dimethoxy-2-nitrobenzyl alcohols attached to various leaving groups: amino acids histidine (NHis) and aspartate (NAsp) as well as their fluorenylmethoxycarbonyl derivatives (FHis) and (FAsp). In addition, two peptides containing either of the two amino acids were studied, carrying the photoreactive group attached to a histidine (PHis), or to an aspartate (PAsp). The aci-nitro forms with maximum at λ(aci) = 420 nm were observed for FHis and FAsp after the decay of a triplet-triplet absorption, analogous to those of other 2-nitrobenzyl type compounds. For both FHis and FAsp the quantum yield of photoconversion Φ(p) is 0.03 and for the peptides PHis and PAsp ca 0.01 and 0.005, respectively.     

Molecular patterning at a liquid/solid interface: the foldamer approach

Molecular patterning has received a lot of attention in the past decade; however, the functionalization of these surface-confined 2D patterns on the nanoscale level remains a challenge. Assembling 2D patterns from oligomeric foldamers turns out to be an interesting approach to accomplishing the controlled positioning of functional elements. We designed a family of peptidomimetic foldamers bearing a 2D turn element folding at the liquid/solid interface. The turning element was developed while studying derivatives with one turning unit. Furthermore, folding was found to be induced by the confinement of the surface. This achievement paves the way for the design of foldamers with multiple turns, providing a higher versatility in the functionalization of nanopatterns.     

Stress relaxation as a microstructural probe for immiscible polymer blends

Relaxation has been investigated in immiscible blends that consist of slightly viscoelastic components. Both the shear and normal stresses have been measured after cessation of steady shear flow as well as after transient shear histories. The latter can generate a fibrillar structure which can relax by either retraction or break-up via end-pinching or Rayleigh instabilities. Each of these three relaxation mechanisms is reflected in the shape of the stress curves, from which also the corresponding structural time scales can be deduced. The experimental results have been used to evaluate the Doi-Ohta and Lee-Park models for immiscible blends. The scaling relations by Doi-Ohta are confirmed by the experimental results, but none of the existing models can correctly predict the complex relaxation behaviour observed for a highly deformed droplet phase. In the present study an alternative approach has been proposed. The stress relaxation due to fibril break-up via Rayleigh instabilities has been predicted successfully by combining physical models for the structural changes with the basic approach of the Doi-Ohta model.     

Penalised spline support vector classifiers: computational issues

We study computational issues for support vector classification with penalised spline kernels. We show that, compared with traditional kernels, computational times can be drastically reduced in large problems making such problems feasible for sample sizes as large as ~10⁶. The optimisation technology known as interior point methods plays a central role. Penalised spline kernels are also shown to allow simple incorporation of low-dimensional structure such as additivity. This can aid both interpretability and performance.     

Mass spectra of some per-O-benzoyl-alditols and -aldobiitols

Electron impact mass spectra of some per-O-benzoyl-alditols and -aldobiitols are reported and the major fragmentation pathways are discussed.