Calculation of macrocyclization equilibria for poly(ethylene terephthalate)

The cyclization equilibria constant K_x is evaluated for the formation of cyclic poly(ethylene terephthalate)s (PET) in the range of degree of polymerization 2 ≤ x ≤ 10 on the basis of an elaborated form of the Jacobson-Stockmayer theory. According to this theory, K_x = W( 0 )·2Γ₀(1)/(σ_cx N_A), where W( r ) is the probability density function for the chain vector r ; Γ₀(γ) is the probability distribution, when r = 0 of γ = cos Δθ; Δθ being the deviation of the bond angle formed by cyclization from its unconstrained value; σ_cx corresponds to the symmetry number of the ring; N_A is Avogadro's number. The evaluation of W( r ) is performed in different approximations. The required configurational averages for computing the density distribution W( r ) and the angular correlation factor Γ₀(1) are obtained by Monte Carlo techniques. The density W( 0 ) of chain vectors at r = 0 is overestimated by the Gaussian approximation. Values of W( 0 ) calculated in higher approximation lower K_x for x < 10. By taking into account the oriental correlation between terminal bonds of the x-meric acyclic sequence, K_x is lowered additionally by factors of ca. 2,2, 1,3 and 1,1 for x = 4, 5 and 6, respectively. Similar to other polymer chains treated so far, K_x is lowered for medium sized chain lengths by taking into account the deviation from Gaussian distribution and angular correlations of chain ends. This result is in contradiction to experimental data, which yield even higher K_x-values than expected by the classical Jacobson-Stockmayer theory for medium sized chain lengths. The inclusion of cis-ester residues into the all trans-ester PET chain only slightly reduces this discrepancy. Structural modifications of the PET chain during cyclization experiments are discussed as a rationale for the deviations from the present theory.     

Linkage analysis of anorexia and bulimia nervosa cohorts using selected behavioral phenotypes as quantitative traits or covariates.

To increase the likelihood of finding genetic variation conferring liability to eating disorders, we measured over 100 attributes thought to be related to liability to eating disorders on affected individuals from multiplex families and two cohorts: one recruited through a proband with anorexia nervosa (AN; AN cohort); the other recruited through a proband with bulimia nervosa (BN; BN cohort). By a multilayer decision process based on expert evaluation and statistical analysis, six traits were selected for linkage analysis (1): obsessionality (OBS), age at menarche (MENAR), and anxiety (ANX) for quantitative trait locus (QTL) linkage analysis; and lifetime minimum body mass index (BMI), concern over mistakes (CM), and food-related obsessions (OBF) for covariate-based linkage analysis. The BN cohort produced the largest linkage signals: for QTL linkage analysis, four suggestive signals: (for MENAR, at 10p13; for ANX, at 1q31.1, 4q35.2, and 8q13.1); for covariate-based linkage analyses, both significant and suggestive linkages (for BMI, one significant [4q21.1] and three suggestive [3p23, 10p13, 5p15.3]; for CM, two significant [16p13.3, 14q21.1] and three suggestive [4p15.33, 8q11.23, 10p11.21]; and for OBF, one significant [14q21.1] and five suggestive [4p16.1, 10p13.1, 8q11.23, 16p13.3, 18p11.31]). Results from the AN cohort were far less compelling: for QTL linkage analysis, two suggestive signals (for OBS at 6q21 and for ANX at 9p21.3); for covariate-based linkage analysis, five suggestive signals (for BMI at 4q13.1, for CM at 11p11.2 and 17q25.1, and for OBF at 17q25.1 and 15q26.2). Overlap between the two cohorts was minimal for substantial linkage signals.     

Observation of a nematic phase displayed by a polysiloxane with trinitrofluorenones as side groups

The synthesis and the results of the structural study of two copolysiloxanes with laterally fixed trinitrofluorenone (TNF) units is reported. The two copolysiloxanes having 2,4 ( 1a ) and 5,3 ( 1b ) dimethylsiloxane comonomer units per TNF side group differ significantly in their phase behaviour as evident from optical microscopy, differential scanning calorimetry and X-ray scattering: 1b shows a nematic mesophase whereas 1a is an amorphous material. The different phase behaviour is discussed in terms of microphase separation between the siloxane backbone and TNF side groups.     

δ-aminolevulinic acid dehydrase (porphobilinogen synthase) in two families with inherited enzyme deficiency

The inheritance of a deficient delta-aminolevulinic acid dehydrase (ALA-D; synonym: porphobilinogen synthase; EC 4.2.1.24) was studied in blood samples of two families over three generations. The propositus in each family was a young male acute hepatic porphyria patient with an almost complete ALA-D deficiency in the homozygous state (ALA-D activity less than 2% of controls). Heterozygotes are clinically non-affected (mean ALA-D 36% of controls). The mode of transmission could be traced by enzyme activity and electrophoretic polymorphism studies. Heterozygotes are detected by the demonstration of enzyme activity in the gel. The notation D was used for the gene expressing the defective enzyme. The "phenotype" D-1 was observed in six, the "phenotype" D-2 in three of all heterozygotes studied. These results are compatible with a single normal allele in heterozygotes responsible for enzyme activity. Quantitative assays and the segregation pattern in both families suggest a 3-allele-system for the inheritance of ALA-D deficiency.     

Polymer diffusion in mixtures of polystyrene and polymethylstyrene studied by forced rayleigh scattering and photon correlation spectroscopy

Tracer diffusion coefficients D^* of both components were measured in mixtures of polystyrene (PS) and polymethylstyrene (PMS), a random copolymer from 60 wt.-% of m-methylstyrene and 40 wt.-% of p-methylstyrene. The results are interpreted in terms of the free-volume theory which yields master curves even for “asymmetric” mixtures of oligomer and polymer chains, if D^* is drawn versus the distance from the glass transition temperature, T–T_g. Whereas D^* was measured by the forced Rayleigh scattering technique, we also studied photon correlation spectroscopy in these mixtures and observed “slow modes” with decay constants that correspond to diffusion coefficients 2–3 decades smaller than the interdiffusion coefficient.     

Über die Grenzbedingungen von Zelleben und spezifischer Zellfunktion am isolierten Muskel

Zusammenfassung 1. Es werden an quergestreiften Muskeln (Zwerchfell, Herzvorhof von Warmblütern, Froschherz) unter den Bedingungen von Substratund Sauerstoffmangel Funktion und histologischer Zustand verglichen.2. Drosselung der Energiezufuhr führt in jedem Falle zu negativer Inotropie und diastolischem Stillstand. Dies führt zu dem zwingenden Schluß, daß die Kontraktion und nicht die Erschlaffung den energieverbrauchenden Teil des Kontraktionsvorganges darstellt.3. Gleichzeitiger Glucose- und Sauerstoffmangel führt erst mit dem Erlöschen der Glykogenolyse zur Kontraktur, die nach völligem Glykogenschwund irreversibel wird (Totenstarre).4. Die Totenstarre wird als Modellkontraktion abgelehnt.5. Aus den untersuchten Mangelbedingungen läßt sich eine Reihenfolge der Energieausnützung für den quergestreiften Muskel ableiten, wobei wesentliche Unterschiede zwischen Warmblüter und Kaltblüter bestehen.Mit 7 Textabbildungen     

Perceptual Performance as a Function of Intra-Cycle Cardiac Activity

The purpose of the experiment was to test the hypothesis of a systematic change in perceptual performance within a single cardiac cycle due to the activity of the baroreceptors in carotid sinus. As an index of perceptual performance the d_s-parameter from signal detection theory (TSD) was used. A 1000 Hz sine tone had to be detected in a background of white noise. Each of 4 subjects received on the average 4605 noise or noise plus tone stimuli distributed over 10 experimental sessions. When comparing performance during time intervals before and after baroreceptor activity onset no significant difference was found. Also, when tracing perceptual performance over the whole cardiac cycle in steps of 66,100, and 200 msec, no systematic variation could be detected. For steps of 33 msec a rhythmic pulsation of perceptual performance of about 8 Hz appeared. An influence of electrical activity of the brain on perceptual performance was postulated. This activity would have to be time-locked to carotid sinus baroreceptor activity.