Orthogonal and parallel superposition measurements on lyotropic liquid crystalline polymers

 Mechanical spectroscopy is used to probe the structure of lyotropic liquid crystalline polymers during flow and after the cessation of flow. The oscillatory flow is either parallel or perpendicular to the steady-state flow. The resulting moduli provide information about the time- and shear-dependent microstructure, including anisotropy. Two different concentrations of poly(benzylglutamate) (PBG) in m-cresol and a concentrated hydroxypropylcellulose (HPC) solution, also in m-cresol, are investigated. In all cases, the orthogonal superposition moduli evolve differently from the parallel ones. The former are less sensitive to the flow-induced changes in structure than the latter ones. Together with the lack of sensitivity of the superposition moduli to texture refinement during flow, this suggests a strong relation between director orientation and superposition moduli. After the cessation of flow the parallel moduli decrease for the PBG solutions, whereas the opposite is observed in the HPC solutions. A comparison with the orthogonal moduli provides a direct measure of anisotropy. At rest, the PBG solutions tend toward a higher degree of anisotropy while the HPC solutions become more isotropic. In the latter systems, all moduli are much larger, reflecting a larger contribution from the texture. Received: 8 July 1999/Accepted: 1 October 1999     

Elastic recovery of immiscible blends Part 2: Transient flow histories

Immiscible polymer blends are known to display an unusual elastic recovery after stress release. Recoil after steady-state shearing is well understood and obeys specific scaling relations. Releasing the stress before the steady-state morphology has been reached results in a more complex elastic recovery, including very large final values. This behaviour is investigated systematically. Model blends are used, consisting of nearly inelastic components; hence the measured recoil can be attributed totally to contributions from the interface. The instantaneous structure at the onset of the recoil can vary greatly in transient experiments, ranging from slightly deformed droplets to highly elongated filaments. The effects of this initial structure on the ultimate recoil and time scale of the recovery are studied. The morphological changes during recovery are considered as well. It is demonstrated that they can be computed from the normal stresses during stress relaxation with comparable initial morphologies. This indicates that the same morphological changes occur during stress relaxation and constrained recoil. A scaling relation for the recoil curves has been derived from the Doi-Ohta theory, which is confirmed by the experiments. Received: 9 December 1998 Accepted: 5 April 1999     

Dynamisches Verhalten von thixotropen Systemen,II

Zusammenfassung Das rheologische Verhalten eines thixotropen Systems wurde als Funktion der momentanen Struktur untersucht. Das System besteht aus Magnesiumsilikat-Fasern, in ein Newtonsches Alkydharz dispergiert. Die Anwendung niedrigfrequenter Schwingungsmessungen in der Analyse solcher Materialien wird diskutiert. Es wird gefunden, daß die charakteristische Zeit für den thixotropen Strukturaufbau um Größenordnungen über dem mittleren Wert der viskoelastischen Relaxationszeit liegt. Es ist daher möglich, das elastoviskose Verhalten der momentanen Strukturen mit Schwingungsmessungen zu erfassen.Mittels dieses Verfahrens wurden Änderungen in dem Relaxationsspektrum, hervorgerufen durch stationäre Strömung, gemessen. Gleichgewichtsstrukturen in stationärer und schwingender Strömung wurden bestimmt, und die Analogie zwischen beiden wurde in dem Falle thixotroper Systeme nachgeprüft. Die Geschwindigkeit des Strukturaufbaus in Ruhe und unter Schwingungen wird betrachtet.

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Summary The rheological behaviour of a thixotropic system has been investigated in terms of the instantaneous structure. The system consists of magnesium silicate fibres, dispersed in a Newtonian. alkyd resin. The application of low frequency oscillatory measurements in the analysis of such materials is discussed. As the characteristic time for thixotropic recovery proved to be several orders of magnitude larger than the average relaxation time, the viscoelastic response of the instantaneous structures can be measured under vibrations of a suitable frequency.Using this technique changes in the relaxation spectrum due to stationary shearing are measured. Equilibrium structures under stationary and oscillatory flow are compared and the similarity principle between both types of measurements is tested for thixotropic systems. The rate of change of thixotropic recovery under rest and under vibrations is considered.

     

Connections between currentπ-electron theories

Connections are given between the theoretical-electron theory in an ordinary atomic orbital basis and semiempirical theories in an orthogonalized basis, neglecting terms of third order. An expression is derived for a one-electron operator with the properties, usually assigned to the effective Hamiltonian of the Hückel method. The non-local part of this operator is shown to give only small contributions also for heteromolecules and lone pairs. Not only short-range forces but also long-range forces, originating from the exchange operator. contribute essentially to the effective bonding. Numerical applications have been madee.g. to aniline andp-benzoquinone.

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Zusammenfassung Es wird der Zusammenhang zwischen einer reinen-Elektronentheorie mit Atomeigenfunktionen als Basis einerseits and semiempirischen Theorien mit orthogonales Basis andererseits aufgezeigt, wobei Glieder dritter Ordnung in Überlappungsintegralen vernachlässigt werden. Dabei läßt sich ein Einelektronenoperator mit den Eigenschaften, die für gewöhnlich für den effektiven Hamiltonoperator der Hückel-Theorie postuliert werden, finden. Sein nichtlokaler Anteil liefert nur geringe Beiträge für Heteroatome und einsame Elektronenpaare. Für die Bindung sind neben den Kräften des Austauschoperators mit kurzer Reichweite auch weitreichende von Bedeutung. Numerische Werte für Anilin undp-Benzochinon werden gegeben.

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Resume Des connections entre la méthode théorique des électrons z sur base d'orbitales atomiques ordinaires, et des théories semiempiriques sur une base orthogonalisée sont données, en négligeant les termes du troisième ordre. On dérive une expression pour un opérateur monoélectronique ayant les propriétés attribuées usuellement à l'opérateur hamiltonien effectif de la méthode de Hückel. On montre que la partie non-locale de cet opérateur ne donne que de contributions petites, même pour les hétéroatomes et les paires libres d'électrons. Non seulement les forces à portée courte, mais aussi celles à portée longue dérivant de l'opérateur d'échange, contribuent essentiellement à Ia liaison effective. Des applications numériques, p.e. pour l'aniline et lep-benzoquinone, ont été effectuées.

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Aided by a research grant to The Johns Hopkins University from the Petroleum Research Fund of the American Chemical Society.     

Toward Artificial Mussel-Glue Proteins: Differentiating Sequence Modules for Adhesion and Switchable Cohesion

Artificial mussel-glue proteins with pH-triggered cohesion control were synthesized by extending the tyrosinase activated polymerization of peptides to sequences with specific modules for cohesion control. The high propensity of these sequence sections to adopt β-sheets is suppressed by switch defects. This allows enzymatic activation and polymerization to proceed undisturbed. The β-sheet formation is regained after polymerization by changing the pH from 5.5 to 6.8, thereby triggering O→N acyl transfer rearrangements that activate the cohesion mechanism. The resulting artificial mussel glue proteins exhibit rapid adsorption on alumina surfaces. The coatings resist harsh hypersaline conditions, and reach remarkable adhesive energies of 2.64 mJ m⁻² on silica at pH 6.8. In in situ switch experiments, the minor pH change increases the adhesive properties of a coating by 300 % and nanoindentation confirms the cohesion mechanism to improve bulk stiffness by around 200 %.     

High-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) for qualitative detection of humic substances and dissolved organic matter in mineral soils and peats in Lithuania

High-performance liquid chromatography (HPLC) with size exclusion (SEC) separation function was used to isolate and examine the molecular mass (MM) distributions and polydispersity of humic substances (HSs) and dissolved organic matter (DOM) from mineral soils and peats. The aim was to improve their detailed characterisation and to inform of their soil carbon (C) sequestration and environmental quality. This is the first study conducted in Lithuania in which HSs and DOM, separated from two soil types, have been used to characterise soil at the molecular level. The HPLC-SEC, as a separation method, was coupled with diode-array detection (DAD), thus enabling the separation of molecular fractions. Results showed that HPLC-SEC can be used to determine the MM of HSs in soil, provided that the relation between retention time and MM is known and a suitable method for fitting the HS peak is available. The UV-spectra analysis showed that DOM has a larger MM (M_w = 2439–3436 Da), which contains more aliphatic C. The HS fraction has a smaller MM (M_w = 2776 Da), with aromatic structures that reflect a higher aromaticity. Separated fractions had characteristic MMs of humic acid (HA) and fulvic acid (FA) and DOM. The HSs separated from peat samples were characterised by higher aromaticity, humification and stability. The HSs extracted from mineral soil samples showed a higher degradability level. The results also show the MM distribution and polydispersity of HS and DOM fractions (M_w/M_n = 1.009–1.252) are relatively homogenous in both soil types. Findings confirm that chromatographic and spectrometric parameters can be used for characterisation of both HSs and DOM, and for detecting changes in organic matter quality. Moreover, they can also be used for a further understanding the C-cycle and could be applied for enhancing soil C-sequestration and informing environmental quality management.     

Reaction pathway to Cu2ZnSnSe4 formation in CdI2

Journal of Thermal Analysis and Calorimetry - We investigated various possible chemical interactions between individual precursor compounds (ZnSe, SnSe, and CuSe) and CdI2 as a flux material used...     

The biogeochemical iron cycle and astrobiology

Biogeochemistry investigates chemical cycles which influence or are influenced by biological activity. Astrobiology studies the origin, evolution and distribution of life in the universe. The biogeochemical Fe cycle has controlled major nutrient cycles such as the C cycle throughout geological time. Iron sulfide minerals may have provided energy and surfaces for the first pioneer organisms on Earth. Banded iron formations document the evolution of oxygenic photosynthesis. To assess the potential habitability of planets other than Earth one looks for water, an energy source and a C source. On Mars, for example, Fe minerals have provided evidence for the past presence of liquid water on its surface and would provide a viable energy source. Here we present Mössbauer spectroscopy investigations of Fe and C cycle interactions in both ancient and modern environments. Experiments to simulate the diagenesis of banded iron formations indicate that the formation of ferrous minerals depends on the amount of biomass buried with ferric precursors rather than on the atmospheric composition at the time of deposition. Mössbauer spectra further reveal the mutual stabilisation of Fe-organic matter complexes against mineral transformation and decay of organic matter into CO₂. This corresponds to observations of a ‘rusty carbon sink’ in modern sediments. The stabilisation of Fe-organic matter complexes may also aid transport of particulate Fe in the water column while having an adverse effect on the bioavailability of Fe. In the modern oxic ocean, Fe is insoluble and particulate Fe represents an important source. Collecting that particulate Fe yields small sample sizes that would pose a challenge for conventional Mössbauer experiments. We demonstrate that the unique properties of the beam used in synchrotron-based Mössbauer applications can be utilized for studying such samples effectively. Reactive Fe species often occur in amorphous or nanoparticulate form in the environment and are therefore difficult to study with standard mineralogical tools. Sequential extraction techniques are commonly used as proxies. We provide an example where Mössbauer spectroscopy can replace sequential extraction techniques where mineralogical information is sought. Where mineral separation is needed, for example in the investigation of Fe or S isotope fractionation, Mössbauer spectroscopy can help to optimize sequential extraction procedures. This can be employed in a large number of investigations of soils and sediments, potentially even for mineral separation to study Fe and S isotope fractionation in samples returned from Mars, which might reveal signatures of biological activity. When looking for the possibility of life outside Earth, Jupiter’s icy moon Europa is one of the most exciting places. It may be just in reach for a Mössbauer spectrometer deployed by a future lander to study the red streak mineral deposits on its surface to look for clues about the composition of the ocean hidden under the moon’s icy surface.