Simulation of the gelation process of hydrogel droplets in 3D bioprinting

The aim of this work is to numerically simulate the gelation of a crosslinking polymer, which is a very complex process involving chemical reactions and phase transitions from a viscous fluid to a viscoelastic solid. A phenomenological model is proposed to simulate the gelation process of agarose droplets, considering the thermal boundary conditions. The numerical model is implemented using the finite element package FlexPDE. The temperature- and time-dependent degree of gelation and the deformation of the droplets during the gelation process are investigated. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

APplication of Continuous Thermodynamics to the Stability of Polymer Systems. II

A determinant criterion for the critical state in solutions and mixtures of polydisperse polymers is established within the general framework of Gibbs theory. The treatment continues an earlier paper by considering more general Gibbs free energy relations: The function replacing the x-term in the classic Flory-Huggins equation is permitted to depend on a finite number of moments of the polymer distribution(s) so as to embrace most Gibbs free energy relations of practical use. The new criterion leads to a very large reduction of computer time and of needed storage capacity compared to the traditional Gibbs determinant criterion. Some relations known from the literature are shown to be special cases of the established new criterion.     

Nucleation of Organic Crystals—A Molecular Perspective

The outcome of synthetic procedures for crystalline organic materials strongly depends on the first steps along the molecular self‐assembly pathway, a process we know as crystal nucleation. New experimental techniques and computational methodologies have spurred significant interest in understanding the detailed molecular mechanisms by which nuclei form and develop into macroscopic crystals. Although classical nucleation theory (CNT) has served well in describing the kinetics of the processes involved, new proposed nucleation mechanisms are additionally concerned with the evolution of structure and the competing nature of crystallization in polymorphic systems. In this Review, we explore the extent to which CNT and nucleation rate measurements can yield molecular‐scale information on this process and summarize current knowledge relating to molecular self‐assembly in nucleating systems.     

Semiconductor Photocatalysis—Mechanistic and Synthetic Aspects

Preceding work on photoelectrochemistry at semiconductor single‐crystal electrodes has formed the basis for the tremendous growth in the three last decades in the field of photocatalysis at semiconductor powders. The reason for this is the unique ability of inorganic semiconductor surfaces to photocatalyze concerted reduction and oxidation reactions of a large variety of electron‐donor and ‐acceptor substrates. Whereas great attention was paid to water splitting and the exhaustive aerobic degradation of pollutants, only a small amount of research also explored synthetic aspects. After introducing the basic mechanistic principles, standard experiments for the preparation and characterization of visible light active photocatalysts as well as the investigation of reaction mechanisms are discussed. Novel atom‐economic C? C and C? N coupling reactions illustrate the relevance of semiconductor photocatalysis for organic synthesis, and demonstrate that the multidisciplinary field combines classical photochemistry with electrochemistry, solid‐state chemistry, and heterogeneous catalysis.     

Site-specific C content by quantitative isotopic C Nuclear Magnetic Resonance spectrometry: A pilot inter-laboratory study

Isotopic ¹³C NMR spectrometry, which is able to measure intra-molecular ¹³C composition, is of emerging demand because of the new information provided by the ¹³C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic ¹³C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular ¹³C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic ¹³C NMR was then assessed on vanillin from three different origins associated with specific δ¹³C_i profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ¹³C_i in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results.     

Freezing and Hydrate Formation in Aqueous Sodium Perchlorate Solutions

The determination of the phase diagram of the binary system sodium perchlorate – water is reported. Beside the eutectic point, two polymorph crystal structures of sodium perchlorate dihydrate were determined. The two crystal structures are discussed, compared to each other and to other known sodiumhalide dihydrate crystal structures. The two polymorphs of the perchlorate dihydrate represent the two variants of connected octahedra in the layer structure found for sodium halide dihydrates.     

Comparative dielectric investigations on samples consisting of fluorinated bent core molecules

Dielectric measurements on four samples composed of bent-shaped molecules with the same basic structure were carried out. They differ only in the position of one fluorine atom in the central core. Two relaxation ranges were detected: the fast reorientation about the long axes and a slow collective process. In three cases, evidence for a positive dipole correlation in the isotropic phase near to the transition to the B₂2 phase was found. All samples show a tendency to give a glass transition. The dielectric constants are discussed in relation to the position of the fluorine atoms.     

Dielectric studies of the 4-n-alkyl-4'-thiocyanatobiphenyl (nBT) homologous series (n=2-10) in the isotropic and E phases

Results of the dielectric studies of nine members of the nBT (4-n-alkyl-4'-thiocyanatobiphenyl, n= 2-10) homologous series in the crystal E (E) and isotropic (I) phases are presented. The dependence of the static permittivity ?_s in the isotropic phase, the longitudinal relaxation times τ_is and τ_∥, and the activation enthalpies ΔH _is and ΔH _∥ on the number of carbon atoms in the alkyl chain n are analysed. A considerable increase in the retardation factor g= τ_∥/τ_is with decreasing n is observed. The results are compared with those obtained for similar two-ring homologous series. The parameters characterizing the molecular rotations around the short axis in the E phase (τ_∥ and ΔH _∥) indicate a hardening of this solid-like phase with shortening of the alkyl chain.     

Dielectric characterization of B3 and B4 phases

Dielectric measurements on two samples formed from banana-shaped molecules with terminal alkyl or alkyloxy groups were carried out in a frequency range between 10^-3 Hz and 10 MHz. Both samples exhibit B₂ and B₃ phases; one of them has a B₄ state as well. As usual, two ranges of relaxation were detected in the B₂ phase, the fast reorientation about the long axes of the molecules and a slow collective process. Only one dielectrically active low frequency process could be separated in the B₃ and B₄ phases; this is probably related to the dynamics of superstructures. The high frequency limit of the dielectric constants gives a hint that neither phase is a classical solid. A quite strong increase in the conductivity at the transition into the B₃ phase is critically discussed.     

Characterization of the B4 phase by dielectric and AFM measurements

Dielectric measurements on a sample consisting of banana-shaped molecules were carried out in a frequency range between 0.1 Hz and 10 MHz. The sample exhibited B₂ and B₄ phases. As usual, two ranges of relaxation were detected in the B₂ phase, the fast reorientation about the long axes of the molecules and a slow collective process. In the B₄ phase, only one dielectric active process at low frequencies was found; this does not differ from the low frequency relaxation of the B₂ modification. This relaxation is probably related to the dynamics of superstructures. Crystallization could be observed after keeping the sample for a longer time at higher temperature. Thus, it was possible to differentiate clearly between the crystalline and the B₄ phases. AFM investigations prove the existence of focal-conic domains and periodic superstructures in the B₄ phase; then do not appear in the crystalline state. For this reason the B₄ phase is regarded as different from a classical crystalline phase.