Die Massenspektren der Pyrrolidide einiger aliphatisch-alicyclischer Carbonsäuren

The mass spectra of the pyrrolidides of some long-chain carboxylic acids with alicyclic residues attached to their ω-end are discussed and compared with the spectra of the corresponding esters. Fragmentation triggered by the pyrrolidide group generates a series of peaks, which clearly exhibits the size and the structure of the carbon chain.     

Photo-stabilization of cis-1,4-polybutadiene with phenylene sulphide oligomers

The new thiooligomers of hydroxyphenylene and hydroxymethoxyphenylene sulphides have been used as photo-stabilizers for cis-1,4-polybutadiene. The photo-stabilizing properties of these thiooligomers were compared with commercial sulphur-containing compounds such as bis(4-hydroxyphenylene)sulphide, 2,2′-thiobis(4-methyl-6-tert.butylphenol) (Irganox 1081), bis((beta-(3,5-di-tert,butyl-4-hydroxybenzyl)-methylcarboxyethyl))sulphide (Irganox 1035) and dilaurylthiodipropionate (Irganox PS800). The photo-stabilizing mechanisms of these compounds have been discussed in detail.     

Determination of triclosan in foodstuffs

A reverse-phase high-performance liquid chromatographic (RP-HPLC) method coupled with an ultraviolet detector was developed to determine triclosan which had migrated into foodstuffs from packaging materials. The method includes extraction with hexane, followed by evaporation to dryness and residue re-dissolution in ACN 90%. Chromatographic separation was performed with a Kromasil 100 C18 column (15 cm x 0.4 cm ID, 5 microm particle size) at 30 degrees C and using ACN and water as mobile phases. Regarding recoveries, good results (higher than 83% and lower than 112%) were obtained for the three representative food matrixes selected (orange juice, chicken breast meat, and Gouda cheese).     

An addition to the oxoacid family: H2B12(OH)12

The acid H(2)B(12)(OH)(12) can be isolated as a crystalline solid by protonation of the hydroxylated borane anion, B(12)(OH)(12)(2)(-). This acidic compound has low solubility in water, conducts protons in the solid state, and has thermal stability to a temperature of 400 degrees C. The conductivity mechanism is a Grotthuss mechanism with a low activation enthalpy (9-13 kcal/mol). This new acid represents an addition to the class of oxoacids, of which sulfuric and phosphoric acid are the most prominent examples.     

Polarographie schwefelhaltiger Proteine

Zusammenfassung An kristallisierten Enzymen des biologischen Stoffwechsel wird gezeigt, daß bei der Polarographie nur die schwefelhaltigen Proteine katalytische Wasserstoffwellen geben. Von den in der Literatur beschriebenen Doppelstufen der Proteine besitzt nur die im negativeren Potentialbereich liegende Welle die eigentliche katalytische Funktion. Die erste Vorwelle von Proteinen verschwindet, wenn die polarographische Messung bei 0° C durchgeführt wird.In Proteinen sind nur Disulfidgruppen katalytisch wirksam. Sogenannte reine Sulfhydryl-Enzyme haben keinen katalytischen Effekt. Typische SH-Enzyme können jedoch polarographisch als p-Chloromercuribenzoatkomplexe gemessen werden.Durch Harnstoffzusatz bei der polarographischen Messung von Proteinen gelingt es, zwischen maskierten und freien Sulfhydryl- oder Disulfidgruppen an Enzymen zu definieren.Auszug aus der Dissertationsschrift H. Katzlmeier, Technische Hochschule München (1959).     

Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies

The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.     

Proton uptake of rhodobacter capsulatus reaction center mutants modified in the primary quinone environment

Flash-induced absorbance spectroscopy was used to analyze the proton uptake and electron transfer properties of photosynthetic reaction centers (RC) of Rhodobacter capsulatus that have been genetically modified near the primary quinone electron acceptor (Q(A)). M246Ala and M247Ala, which are symmetry-related to the positions of two acidic groups, L212Glu and L213Asp, in the secondary quinone electron acceptor (QB) protein environment, have been mutated to Glu and Asp, respectively. The pH dependence of the stoichiometry of proton uptake upon formation of the P+Q(A)- (H+/P+Q(A)-) and PQ(A) (H+/Q(A)-) (P is the primary electron donor, a noncovalently linked bacteriochlorophyll dimer) states have been measured in the M246Ala --> Glu and the M247Ala --> Asp mutant RC, in the M246Ala-M247Ala --> Glu-Asp double mutant and in the wild type (WT). Our results show that the introduction of an acidic group (Glu or Asp) in the QA protein region induces notable additional proton uptake over a large pH region (approximately 6-9), which reflects a delocalized response of the protein to the formation of Q(A)-. This may indicate the existence of a widely spread proton reservoir in the cytoplasmic region of the protein. Interestingly, the pH titration curves of the proton release caused by the formation of P+ (H+/P+: difference between H+/P+Q(A)- and H+/PQ(A)- curves) are nearly superimposable in the WT and the M246Ala --> Glu mutant RC, but substantial additional proton release is detected between pH 7 and 9 in the M247Ala --> Asp mutant RC. This effect can be accounted for by an increased proton release by the P+ environment in the M247Ala --> Asp mutant. The M247Ala --> Asp mutation reveals the existence of an energetic and conformational coupling between donor and acceptor sides of the RC at a distance of nearly 30A.     

Kinetics of lamellar-to-cubic and intercubic phase transitions of pure and cytochrome c containing monoolein dispersions monitored by time-resolved small-angle X-ray diffraction

We investigated the effect of incorporation of a small aqueous peripheral membrane protein (cyt c) into the three-dimensional periodic nanochannel structures formed by the lipid monoolein (MO) on its rich phase behavior as a function of temperature, pressure, and protein concentration using synchrotron X-ray small-angle diffraction. By simultaneous use of the pressure-jump relaxation technique and time-resolved synchrotron X-ray diffraction, we also studied the kinetics of various lipid mesophase transformations of the system for understanding the mechanistic pathways of their formation influenced by the protein-lipid interactions. Cyt c incorporated into the bicontinuous cubic phase Ia3d of MO has a significant effect on the lipid structure and the pressure stability of the system already at low protein concentrations. Concentrations higher than 0.2 wt % of cyt c led to an increase in interfacial curvature due to interaction of the protein with the lipid headgroups. This promotes the formation of a new, probably partially micellar cubic phase of crystallographic space group P4(3)32. Upon pressurization, the P4(3)32 phase undergoes a phase transition to a cubic Pn3m phase with smaller partial specific volume. Increase in protein concentration increases the pressure stability of the P4(3)32 phase. The formation of this phase from the cubic phase Pn3m is a slow process taking many seconds and having a time lag in the beginning. It seems to occur as a two-state process without ordered intermediate states. At temperatures above 60 degrees C, the P4(3)32 phase is unable to accommodate the unfolded protein and transforms to a bicontinuous cubic Ia3d phase. Time-resolved small-angle X-ray scattering studies show that the L(alpha) --> Ia3d transition in pure MO dispersions under limited hydration conditions occurs within a time interval of 1 s at 35 degrees C preceded by a lag phase of 1.5 s. The Ia3d cubic phase initially forms with a much larger lattice constant due to hydration and experiences an initially lower curvature that relaxes within about 1 s. Interestingly, no other cubic phases are involved as intermediates in the transition, i.e., the gyroid cubic phase is able to form directly from the L(alpha) phase. The mechanism behind the L(alpha) --> Ia3d transition in pure MO dispersions has been discussed within the framework of recent stalk models for membrane fusion. In the presence of cyt c, the L(alpha) --> Ia3d transition is much slower. The rather long relaxation times of the order of seconds are probably due to a kinetic trapping of the system and limitation by the transport and redistribution of water and lipid in the evolving new lipid phases. We also studied the transition from the pure lamellar L(alpha) phase to the Ia3d-P4(3)32 two phase region and observed a rather complex transition behavior with transient lamellar and cubic intermediate states.     

Solvation structure of hydroxyl radical by Car-Parrinello molecular dynamics

Car-Parrinello molecular dynamics simulations of a hydroxyl radical in liquid water have been performed. Structural and dynamical properties of the solvated structure have been studied in details. The partial atom-atom radial distribution functions for the hydrated hydroxyl do not show drastic differences with the radial distribution functions for liquid water. The OH is found to be a more active hydrogen bond donor and acceptor than the water molecule, but the accepted hydrogen bonds are much weaker than for the hydroxide OH- ion. The first solvation shell of the OH is less structured than the water's one and contains a considerable fraction of water molecules that are not hydrogen bonded to the hydroxyl. Part of them are found to come closer to the solvated radical than the hydrogen bonded molecules do. The lifetime of the hydrogen bonds accepted by the hydroxyl is found to be shorter than the hydrogen bond lifetime in water. A hydrogen transfer between a water molecule and the OH radical has been observed, though it is a much rarer event than a proton transfer between water and an OH- ion. The velocity autocorrelation power spectrum of the hydroxyl hydrogen shows the properties both of the OH radical in clusters and of the OH- ion in liquid.