Proton relaxation times in human red bone marrow by volume selective magnetic resonance spectroscopy

In hematological diseases the composition of red bone marrow shows alterations. The relaxation timesT ₁ andT ₂ of water and lipids in human hemopoietic bone marrow of 14 normal volunteers and 10 patients with acute leukemia and bone marrow carcinosis are determined using a double spin echo spectroscopy sequencein vivo. The volumes of interest (VOI) of (13 mm)³ in the center of vertebral bodies are examined using different measurement parameters. ForT ₁ measurements an inversion-recovery method is used.T ₂ is evaluated from spectra with differentTE. T ₁ (water) is found in a range between 1000 and 1700 ms,T ₁ (lipids) in a range between 260 and 320 ms in healthy volunteers.T ₂ (water) is determined between 32 and 65 ms. In some cases phase distortions of the water signals occur in the spectra. Water flow within the VOI may be a possible reason.T ₂ (lipids) is evaluated between 73 and 91 ms. The patients with acute leukemia exhibit clearly reduced lipid signals in their spectra. Lipid relaxation times could not be determined in these cases.T ₂ (water) is prolonged in acute leukemia to 51–98 ms.T ₁ (water) was not significantly different from values of healthy volunteers in our measurements. Results are discussed in comparison to relaxometric data from imaging and STEAM spectroscopic methods of other authors.     

Differential AC-chip calorimeter for glass transition measurements in ultrathin films

A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006     

Bilayer studies in mixedn-decanol/n-tetradecanol complexes ofn-decylammonium beidellite

Complexes have been prepared by treatment ofn-decylammonium beidellite with mixtures ofn-decanol andn-tetradecanol with different concentrations. Measurements of the basal spacings of the obtained complexes have been performed in a wide range of temperatures. Three different bilayer phases have been established between (20 and 70°C: the _i(C₁₀) phases (=bilayers ofn-decyl chains); the _i(C₁₀/C₁₄) phases (=mixed bilayers ofn-decyl andn-tetradecyl chains in molar ratio approximately 1:1) and the _i(C₁₄) phases (=bilayer ofn-tetradecy 1 chains with then-decylammonium ions included). In all bilayer phases the chains stand perpendicular to the silicate interfaces. In definite concentration ranges two of the phases coexist, i.e., miscibility gaps occur, which disappear at temperatures higher than the temperature of the _i/ transition. The miscibility gaps are reversible with temperature. The composition of the intercalated bilayers has been studied by HPLC of the excess alkanol mixture separated from the beidellite complexes after the equilibrium has been reached. There is preferential adsorption of one of two alkanols from the mixture, which is in agreement with the observed miscibility gaps. The space filling problem as well as the structure of the three bilayer phases observed have been discussed.     

Superheating in linear polymers studied by ultrafast nanocalorimetry

To study phase transition kinetics on submillisecond time scale a sensitive ultrafast nanocalorimeter was constructed. Controlled ultrafast cooling, as well as heating, up to 10⁶K/s was attained. The method was applied for the measurements of the superheating phenomenon in a set of linear polymers: iPS, PBT, PET, and iPP. A power law relation between the superheating and the heating rate holds in the heating rate range 10^-2-10⁴K/s. A limiting superheating of about 10% of the melting temperature was observed at rates above 10⁴-10⁵K/s. This limit depends on annealing conditions before sample melting. The observed superheating limit, as well as the power law, can be accounted for the internal stresses near the crystalline amorphous interface in semicrystalline polymers induced by heating, which are related to the thermal expansion gradients inherent in a semicrystalline material.