Second Dissociation Constants of 4-[N-morpholino]butanesulfonic Acid and N-[2-hydroxyethyl]piperazine-N′-4-butanesulfonic Acid from 5 to 55°C

The values of the second dissociation constant, pK ₂, for the dissociation of the NH⁺ charge center of the zwitterionic buffer compounds 4-(N-morpholino)butanesulfonic acid (MOBS), and N-(2-hydroxyethyl)piperazine-N-4-butanesulfonic acid (HEPBS) have been determined from 5 to 55°C, including, 37°C at intervals of 5°C. The electromotive-force (emf) measurements have been made utilizing hydrogen electrodes and silver–silver chloride electrodes. The value of pK ₂ for MOBS was found to be 7.702 ± 0.0005, and 8.284 ± 0.0004 for HEPBS, at 25°C, respectively. The related thermodynamic quantities, G ^o, H ^o, S ^o, and C _p ^o for the dissociation processes of MOBS and HEPBS have been derived from the temperature coefficients of pK ₂. Both the MOBS and HEPBS buffer materials are useful as primary pH standards for the control of pH 7.3 to 8.6 in the region close to that of physiological fluids.     

Crystal and molecular structure ofS-methyl(pentafluorosulfanyl)thiocarbamate

The X-ray structure of S-methyl(pentafluorosulfanyl)thiocarbamate, SF₅NHC(O)SCH₃, has been determined from three-dimensional diffractometer data and refined by full-matrix least-squares techniques. The crystals are monoclinic:P2₁/m,a=5.008 (5),b=7.811 (2),c=9.348 (4) Å, =99.08 (7)°, andZ=2; finalR=0.046 for 517 observed reflections. The structure comprises hydrogen-bonded (NHO) chains with the component monomers in thecis, cis-conformation, i.e., the arrangement of the nonhydrogen and nonfluorine atoms is nearly planar, the SF₅ group and the O are in acis position with respect to the C-NH bond, and the O and the CH₃ group are in acis position with respect to the C(O)-S bond. Theoretical methods including MNDO and molecular modeling were used to study the relative stabilities of the four possible conformations of SF₅NHC(O)SCH₃.     

CO laser stabilization using the optogalvanic Lamb-dip

Frequency stabilization of the CO laser using a CO lamb-dip is achieved in the range from 5.0–6.3 m. The CO saturation signal is obtained from a low-pressure discharge in absorption and is detected using optogalvanic, detection. The frequency stability and reproducibility has been verified to be better than 100 kHz; this is an improvement of more than one order of magnitude compared with locking techniques using CO laser gain profiles.Alexander von Humboldt Awardee from National Bureau of Standards, Boulder, Colorado, USA     

Analysis of the 3-dimensional electron distribution in silicon using directional Compton profile measurements

A method of reconstructing the electron momentum density (p), and its Fourier transform,B(t), from a series of directional Compton profiles is described. It is based on a double Fourier inversion technique and an expansion in lattice harmonic functions. The effect of random errors has been analysed, and the implications for the data collection discussed. We have used the reconstruction technique to obtain (p) andB(t) for silicon from six directional Compton profiles measured with 412 KeV gamma-radiation. The experimental result is in good agreement with earlier measurements and with available solid state theories. A recent Wannier function calculation for silicon using orthogonalised bond orbitals provides a useful tool for identifying the physical origins of the observed anisotropies. A comparison between the information presented in position and momentum space shows that the ease of interpretation depends upon the degree to which the various interactions give rise to localised features in each representation.     

Lifshitz tails for periodic plus random potentials

We prove that the integrated density of states () for a potentialW =V _per +V has Lifshitz tails where V_per is a periodic potential with reflection symmetry andV is a random potential, e.g., of the formV =q _i ()f(x–i).research partially supported by DFG.research partially supported by USNSF under grant No. MCS-81-20833.     

Characterization of the Fe(III)‐binding Site in Sepia Eumelanin by Resonance Raman Confocal Microspectroscopy¶

The resonance Raman spectrum of Sepia eumelanin is discussed by analogy to model compounds containing catechol (CAT)‐like structural units. These data are then compared with the analogous data on Fe(III)‐enriched Sepia eumelanin. In contrast to the natural eumelanin, the Fe(III)‐enriched samples exhibit absorption features in the visible and near‐IR spectral regions, which are attributed to ligand‐to‐metal charge‐transfer (LMCT) bands. Resonance Raman spectra collected by exciting these LMCT bands reveal bands at 580 and 1470 cm^?1; the intensity of these features increases wioth increasing Fe(III) content. The 580 and 1470 cm^?1 bands are assigned to Fe‐OR stretching and ring deformation modes, respectively. These data further substantiate that the Fe(III)‐ melanin‐binding site in melanin is composed of CAT‐like structural units.