Use of monomer fraction data in the parametrization of association theories

Association theories such as the CPA (cubic-plus-association), NRHB (non-random hydrogen bonding) equations of state and the various variants of SAFT (statistical associating fluid theory) have been extensively applied to phase equilibrium calculations. Such models can also be used for estimating the monomer fraction of hydrogen bonding compounds and their mixtures. Monomer fraction data are obtained from spectroscopic measurements and they are available for a few compounds such as pure water and alcohols as well as for some alcohol–alkane and similar mixtures. These data are useful for an understanding of the capabilities and limitations of association models. The purpose of this work is two-fold: (i) to compare the performance of three models, CPA, NRHB and sPC-SAFT, in predicting the monomer fraction of water, alcohols and mixtures of alcohol-inert compounds and (ii) to investigate whether “improved” model parameters can be obtained if monomer fraction data are included in the parameter estimation together with vapor pressures and liquid densities. The expression “improved” implies parameters which can represent several pure compound properties as well as monomer fraction data for pure compounds and mixtures. The accuracy of experimental monomer fraction data is discussed, as well as the role of monomer fraction data in clarifying which association scheme should be used in these equations of state. The results reveal that the investigated association models (CPA, sPC-SAFT and NRHB) can predict, at least qualitatively correct, monomer fractions of associating compounds and mixtures. Only, small differences are observed between the models. In addition, it has been shown that, using a suitable association scheme, a single set of parameters can describe satisfactorily vapor pressures, liquid densities and monomer fractions of water and alcohols. The 4C scheme is the best choice for water, while for methanol there is small difference between the 2B and 3B association schemes.     

Understanding the effect of cobalt particle size on Fischer-Tropsch synthesis: surface species and mechanistic studies by SSITKA and kinetic isotope effect

Co/γ-Al(2)O(3) catalysts with particle sizes in the range of 4-15 nm were investigated by isothermal hydrogenation (IH), temperature programmed hydrogenation (TPH), and steady-state isotopic transient kinetic analysis (SSITKA). Kinetic isotope effect experiments were used to probe possible mechanisms on Co/γ-Al(2)O(3) with different particle size. It was found that CO dissociated on Co/γ-Al(2)O(3) catalysts at 210 °C. The total amount of CO(2) formed following the dissociation depends on the cobalt crystal size. O-Co binding energy was found to be highly dependent on the Co metal particle size, whereas similar C-Co binding energy was found on catalysts with different Co particle size. Very strongly bonded carbon and oxygen surface species increased with decreasing particle size and acted as site blocking species in the methanation reaction. SSITKA experiments showed that the intrinsic activity (1/τ(CH(x))) remained constant as the particle size increased from 4 to 15 nm. The number of surface intermediates (N(CH(x))) increased with increasing particle size. The apparent activation energies were found similar for these catalysts, about 85 kJ/mol. D(2)-H(2) switches further confirmed that the particle size did not change the kinetically relevant steps in the reaction. The reactivity of the active sites on the 4 nm particles was the same as those on the 8, 11, and 15 nm particles, and only the number of total available surface active sites was less on the 4 nm particles than on the others.     

Synthesis of a small library of non-symmetric cyclic sulfamide HIV-1 protease inhibitors

A set of 11 non-symmetric cyclic sulfamide HIV-1 protease inhibitors were synthesized and evaluated. The use of a key microwave-assisted silver(I) oxide mediated selective mono N-benzylation reaction enabled fast and straightforward synthesis. The K_i values of the new inhibitors ranged between 0.28 μM and >20 μM.     

Slow dynamics of a colloidal lamellar phase

We used x-ray photon correlation spectroscopy to study the dynamics in the lamellar phase of a platelet suspension as a function of the particle concentration. We measured the collective diffusion coefficient along the director of the phase, over length scales down to the interparticle distance, and quantified the hydrodynamic interaction between the particles. This interaction sets in with increasing concentration and can be described qualitatively by a simplified model. No change in the microscopic structure or dynamics is observed at the transition between the fluid and the gel-like lamellar phases.     

Accelerated 18O-labeling in urinary proteomics

Proteolytic (18)O-labeling of peptides has been studied and optimized in order to improve the labeling efficiency and to accelerate the process without increasing the degree of incomplete labeling. Using peptides generated from tryptic digested bovine serum albumin (BSA) and cytochrome c as model proteins, it was shown that complete labeling was achieved after 2 h at pH 6. To increase the sample throughput in a bottom-up proteomic setup, tryptic digestion of proteins in-solution was replaced with tryptic digestion using immobilized trypsin. As a result, an integrated approach was made possible, where both digestion (pH 8) and (18)O/(16)O-labeling of the resulting peptides (pH 6) were done using immobilized trypsin beads. This simplified the sample handling and reduced the overall reaction time significantly: the setup enabled tryptic digestion and (18)O/(16)O-labeling without sample transfer steps within 3.5 h with average (18)O/(16)O-ratios of 0.96±0.13 in aqueous buffer. The initial results were confirmed with a more complex matrix, by spiking urine with the model proteins, yielding results comparable with the ratios obtained in buffer. Satisfying ratios were also achieved regarding urinary proteins identified in a full scale bottom-up experiment. Average (18)O/(16)O-peptide ratios of 0.83±0.13 and 0.91±0.27 indicated good performance in a highly relevant matrix for biomarker discovery.     

Vowel-related tongue movements in speech: straight or curved paths? (L)

This paper examines tongue movements between the two vowels in sequences of vowel-labial consonant-vowel, addressing the question whether the movement is a straight line or a curved path. Native speakers of Japanese and Italian served as subjects. The linguistic material consisted of words where the bilabial consonant was either long or short. The inclusion of words with different consonant lengths was motivated by earlier findings that the tongue movement is often longer when the consonant is long, which may be due to a more curved movement path. Tongue movements were recorded using a three-transmitter magnetometer system. To assess the movement path, the movement magnitude was calculated in two ways, as a straight line, the Euclidean distance, and as the actual path, obtained by summing the individual Euclidean distances between successive samples from movement onset to offset. The ratio between the path and the Euclidean distance is 1 when the movement is a straight line and greater than 1 when the path is curved. Results show that in virtually all 21 cases examined the ratio was very close to 1 and in most cases 1.2 or less. There was no reliable influence of consonant length on the ratio.     

Potential solutions to improved sound performance of volume based lightweight multi-storey timber buildings

Lightweight building systems in general suffer from poor sound insulation, especially in the low frequency region. Since no reliable mathematical models that can predict the impact sound pressure level exists, the lightweight building design is to a high extent based upon previous experience and upon measurements. A special difficulty is related to experimental measurements since the variation among identical units must not be neglected. A modern volume based lightweight wooden building concept has here been tested by numerous well controlled measurements, in laboratory as well as in more field like conditions. The volume construction technique offers new possibilities and challenges to improve sound insulation in light weight timber construction. The main purpose was to investigate how different constructional solutions in the floor, like plaster board, mineral wool, elastic glue, dividing board, floating floor etc., affect the sound insulation. Many of the tested modifications resulted in only marginally changed impact sound pressure level but parameters that substantially can improve the sound insulation were found in using elastic glue to mount the floor boards, to install extra board layers and to use floating floors.     

Experimental determination of the ²⁴Mg I (3s3p)³P₂ lifetime

We present the first experimental determination of the electric-dipole forbidden (3s3p)3P?→(3s2)1S? (M2) transition rate in 2?Mg and compare to state-of-the-art theoretical predictions. Our measurement exploits a magnetic trap isolating the sample from perturbations and a magneto-optical trap as an amplifier converting each 3P?→1S? decay event into millions of photons readily detected. The transition rate is determined to be (4.87 ± 0.3)×10?? s?1 corresponding to a 3P? lifetime of 2050(-110)(+140) sec. This value is in agreement with recent theoretical predictions, and to our knowledge the longest lifetime ever determined in a laboratory environment.     

Shape of the ferromagnetic resonance absorption band of textured powder samples of maghemite

The shape of the ferromagnetic resonance absorption band of powder microcrystalline ferrite γ-Fe₂O₃ has been studied. Samples in the form of a ferromagnetic fluid have been subjected to preliminary particle orientation and frozen in a magnetic field. The shape of the absorption bands has been computer processed with allowance for the anisotropy of the shape of particles and their spatial cubic anisotropy, as well as for the contribution from nondispersed fraction of the bulk of the powder. Satisfactory agreement with the experiment has been obtained for several orientations of the measuring magnetic field with respect to the preliminary orientation.     

A fully integrated IQ-receiver for NMR microscopy

We present a fully integrated CMOS receiver for micro-magnetic resonance imaging together with a custom-made micro-gradient system. The receiver is designed for an operating frequency of 300 MHz. The chip consists of an on-chip detection coil and tuning capacitor as well as a low-noise amplifier and a quadrature downconversion mixer with corresponding low-frequency amplification stages. The design is realized in a 0.13 μm CMOS technology, it occupies a chip area of 950 × 800 μm2 and it draws 50 mA from a supply voltage of 1.8 V. The achieved time-domain spin sensitivity is 5×10(14)spins/Hz. Images of phantoms obtained in our custom-made gradient system with 8 μm isotropic resolution are reported.