Dual-cure processes: towards deformable crosslinked coatings

Two dual-cure processes consisting of a UV-initiated radical polymerization followed by either a UV-induced cationic polymerisation, or a thermal addition reaction, were investigated. The feasibility of the processes was studied using an acrylate-oxetane monomer for the UV/UV combination, and an acrylated oligoester for the UV/Heat combination. It was shown by FTIR and Tg measurements, that both steps of each process could be performed efficiently and separately. This allowed the production of a deformable partially cured coating, whose cure can then be completed, leading to the required final properties. Furthermore, it was demonstrated that the increase of the functionality of the reactive diluent led to a decrease of the thermal crosslinking extent. This is probably due to the reduced mobility of the reactive species that is caused by an enhanced UV crosslinking taking place during the first step.     

Thermal relaxation in poled non-linear optical sidechain polymers: Influence of annealing

The influence of different annealing treatments has been investigated on the stability of the Electro-Optic coefficient in a poled DANS (4-dimethylamino-4′-nitrostilbene) sidechain polymer, which was poled near its T_g-onset of 140°C. The annealing treatments and the EO relaxation experiments were performed at 120°C. The EO stability can be significantly increased both by an annealing treatment after poling and by annealing before poling. This latter effect is concluded from the reduction of the EO relaxation rates in successive relaxation cycles performed in the same polymer sample - completely depoled and repoled in between the cycles. The effect from the different annealing treatments on the time-dependence of the EO relaxation process is different and is analyzed in terms of a Debye-like model with a single, time-dependent Debye relaxation time r(t)=r_i+C. t³. The time-dependence of r and the observed effects from annealing are attributed to the parallel relaxation process of physical ageing.     

Investigating direct current potentials that affect native protein conformation during trapped ion mobility spectrometry–mass spectrometry

Trapped ion mobility spectrometry–time-of-flight mass spectrometry (TIMS-TOFMS) has emerged as a tool to study protein conformational states. In TIMS, gas-phase ions are guided across the IM stages by applying direct current (DC) potentials (D1–6), which, however, might induce changes in protein structures through collisional activation. To define conditions for native protein analysis, we evaluated the influence of these DC potentials using the metalloenzyme bovine carbonic anhydrase (BCA) as primary test compound. The variation of DC potentials did not change BCA-ion charge and heme content but affected (relative) charge-state intensities and adduct retention. Constructed extracted-ion mobilograms and corresponding collisional cross-section (CCS) profiles gave useful insights in (alterations of) protein conformational state. For BCA, the D3 and D6 potential (which are applied between the deflection transfer and funnel 1 [F1] and the accumulation exit and the start of the ramp, respectively) had most profound effects, showing multimodal CCS distributions at higher potentials indicating gradual unfolding. The other DC potentials only marginally altered the CCS profiles of BCA. To allow for more general conclusions, five additional proteins of diverse molecular weight and conformational stability were analyzed, and for the main protein charge states, CCS profiles were constructed. Principal component analysis (PCA) of the obtained data showed that D1 and D3 exhibit the highest degree of correlation with the ratio of folded and unfolded protein (F/U) as extracted from the mobilograms obtained per set D potential. The correlation of D6 with F/U and protein charge were similar, and D2, D4, and D5 showed an inverse correlation with F/U but were correlated with protein charge. Although DC boundary values for induced conformational changes appeared protein dependent, a set of DC values could be determined, which assured native analysis of most proteins.     

Extrinsic multiecho phase-contrast SSFP: evaluation on cardiac output measurements

Multiecho phase-contrast steady-state free precession (PC-SSFP) is a recently introduced sequence for flow quantification. In this multiecho approach, a phase reference and a velocity-encoded readout were acquired at different echo times after a single excitation. In this study, the sequence is validated in vitro for stationary flow. Subsequently, the sequence was evaluated on cardiac output measurements in vivo for through-plane flow in comparison to regular single gradient echo velocity quantification [phase-contrast spoiled gradient echo (PC-GE)]. In vitro results agreed with regular flow meters (RMS 0.1 cm/s). Cardiac output measurements with multiecho PC-SSFP on 10 healthy subjects gave on average the same results as the standard PC-GE. However, the limits of repeatability of PC-SSFP were significantly larger than those of PC-GE (2 l/min and 0.5 l/min, respectively, P=.001). The multiecho approach introduced some specific problems in vivo. The difference in echo times made the velocity maps sensitive for water-fat shifts and B(0)-drifts, which in turn made velocity offset correction problematic. Also, the addition of a single bipolar gradient cancelled the flow compensated nature of the SSFP sequence. In combination with the prolonged TR, this resulted in flow artifacts caused by high and pulsatile through-plane flow, affecting repeatability. Given the significantly lower repeatability of PC-SSFP, cardiac output in turn is less reliable, thus impairing the use of multiecho PC-SSFP.     

Superhydrophobic surfaces having two-fold adjustable roughness prepared in a single step

A fast and reliable method is reported for fabricating superhydrophobic surfaces. The method combines microstructure replication with polymer phase inversion and can be applied to a wide variety of polymers. This method provides a surface that contains roughness on two independently controllable levels, i.e., the microstructure level and the level of porosity stemming from the phase inversion. Both levels were optimized separately, resulting in water contact angles up to 167 degrees.     

Towards the automatic analysis of NMR spectra: part 6. Confirmation of chemical structure employing both 1H and 13C NMR spectra

A method of comparing predicted and experimental chemical shifts was used to confirm or refute postulated structures. 1H NMR spectra returned all true positives with a false positive rate of 4%. When an analogous procedure was adopted for 13C NMR spectra, the false positive rate dropped to 1%, whereas the more practical HSQC data yielded a false positive rate of 2%. If the HSQC results were combined with 1H results, a false positive rate of 1% resulted, 4 times more accurate than 1H alone.     

Polymer-in-a-silica-crust membranes: macroporous materials with tunable surface functionality

We report on alkaline hydrolysis of tetraethoxysilane (St?ber synthesis) inside a macroporous polymer matrix resulting in a homogeneous coverage of silica onto the polymer surface. The encapsulation of the polymer struts by a continuous silica crust allows further functionalization with hydrophilic and hydrophobic silylating agents. The porous silica polymeric hybrid material combines the morphological control and mechanical flexibility of the polymeric matrix with the convenient surface modifications developed for glass and amorphous silica. This concept is applied to macroporous membranes where alteration in surface functionality allows tuning of hydrophobicity (contact angle and liquid entry pressure), streaming potential, and adsorption capacity of double-stranded DNA.     

Multicomponent synthesis of dihydropyrimidines and thiazines

A broad range of differently substituted dihydropyrimidines and thiazines can be efficiently prepared by using a four-component reaction between phosphonates, nitriles, aldehydes, and iso(thio)cyanates. The scope and limitations of this multicomponent reaction are fully described. Variation of all four components has been investigated. The nitrile and aldehyde inputs can be varied extensively, but variation of the phosphonate input remains limited. An interesting rearrangement leading to phosphoramidates has been observed. Furthermore, the multicomponent reaction seems to be restricted to the use of isocyanates with strongly electron-withdrawing substituents, but an interesting additional exchange reaction under microwave conditions leads to dihydropyrimidines with less electron-withdrawing substituents at N3. In addition, a diastereoselective formation of dihydropyrimidines has been observed when using a chiral aldehyde as the input. Finally, by changing the isocyanate component to an isothiocyanate, thiazines are efficiently formed instead of the corresponding thio-dihydropyrimidines.