4.50—Polarographic investigation of conformational changes of human serum albumin: Part I. Unfolding of human serum albumin by urea

The mechanism of the unfolding of human serum albumin by urea was studied using d.c. polarography. It was found that this reaction is a complex process which cannot be described in terms of a two-state transition model. As well as the Brdi?ka catalytic current we have also studied the reduction current of disulfide groups in native and denatured human serum albumin. The number of cystine residues accessible for electrode reduction in native and denatured protein was calculated. On the basis of these results a scheme for the unfolding of human serum albumin by urea is proposed.     

Composition of the basic fraction of marijuana and tobacco condensates: A comparative study by capillary GC/MS

Summary Combined capillary gas chromatography/mass spectrometry has been used to characterize the basic fraction of Mexican marijuana and standard tobacco smoke condensates. A thermostable Superox-coated glass capillary column permitted elution of relatively large nitrogen-containing compounds. Substantial qualitative and quantitative differences between the two materials were noted.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.     

Quantum-Chemical Study of the Relative Stability of N-Substituted Tetrazole Isomers

The enthalpies of formation and total energies of a series of 1- and 2-substituted tetrazoles in the gas phase and in solution were calculated by MNDO and AM1 semiempirical methods and by a set of nonempirical procedures. The effect of solvent on the relative stability of N-substituted tetrazoles was estimated in terms of the PCM, SM5, and SCRF models. The possibility for isomerization of N-substituted tetrazoles, depending on the substituent in position 1 or 2, was studied at the MP2/6-31G*//HF/6-31G* level. According to the results of nonempirical calculations, 2-substituted tetrazoles are more stable in the gas phase, in keeping with the experimental data for the corresponding isomers. The solvent nature is an important factor affecting isomerization of N-substituted tetrazoles: Rise in the solvent polarity leads to displacement of the equilibrium toward 1-substituted isomers.     

Separation of fluorescent oligosaccharide derivatives by microcolumn techniques based on electrophoresis and liquid chromatography.

Various aldose oligosaccharides can be quantitatively derivatized into primary amines for subsequent reaction with fluorogenic reagents, such as 3-(4-carboxybenzoyl)-2-quinolinecarboxaldehyde or 3-benzoyl-2-naphthaldehyde. Capillary electrophoresis (CE) and microcolumn liquid chromatography (LC), coupled with laser-induced fluorescence detection, were evaluated as a means of separating complex oligosaccharide mixtures. Whereas microcolumn LC and open-tubular CE appear confined in their utility to relatively small oligosaccharides, unprecedented results were obtained with polyacrylamide gel-filled capillaries on hydrolyzed malto-oligosaccharides and enzymatically degraded samples of chondroitin sulfate and hyaluronic acid.     

Applications of a miniaturized fluorimetric photodiode array detector for capillary liquid chromatography

A high sensitivity, multichannel fluorescence detector with small volume has been developed for capillary column liquid chromatography. Using an intensified linear photodiode array to monitor fluorescence emission, several important mixtures exhibiting native fluorescence have been examined following high efficiency separation on a capillary column. By correlating mass spectral, fluorescence spectral, and retention time data, information of potential utility in the structural elucidation of aromatic molecules contained in complex mixtures can be obtained. Examples include the separation and spectral examination of the polyaromatic compounds in samples of both biological and environmental interest.     

57Fe Mössbauer study of amorphous and nanocrystalline Fe73.5Nb3Cu1Si13.5B9 after neutron irradiation

⁵⁷Fe Mössbauer spectroscopy is used to study neutron irradiation induced changes in the short-range order of Fe_73.5Nb₃Cu₁Si_13.5B₉ alloy. The samples are investigated in both amorphous and nanocrystalline states. Neutron irradiation leads to an increase of the standard deviation of a hyperfine field distribution (HFD), implying rearrangement of the atoms towards disordering. Simultaneously, changes in the average value of the hyperfine field and a net magnetic moment position occur as a consequence of a spin reorientation, atom mixing and microscopic stress centres which are introduced by neutron irradiation.