High frequency alternating current chip nano calorimeter with laser heating.

Heat capacity spectroscopy at frequencies up to 100 kHz is commonly performed by thermal effusivity measurements applying the 3ω-technique. Here we show that AC-calorimetry using a thin film chip sensor allows for the measurement of frequency dependent heat capacity in the thin film limit up to about 1 MHz. Using films thinner than the thermal length of the thermal wave (~1 µm) at such frequencies is advantageous because it provides heat capacity alone and not in combination with other quantities like thermal conductivity, at least on a qualitative basis. The used calorimetric sensor and the sample are each less than 1 µm thick. For high frequency AC-calorimetry, high cooling rates at very small temperature differences are required. This is realized by minimizing the heated spot to the size of the on chip thermocouple (3 × 6 µm(2)). A modulated laser beam shaped and positioned by a glass fiber is used as the heat source. The device was used to measure the complex heat capacity in the vicinity of the dynamic glass transition (structural relaxation) of poly(methyl methacrylate). Combining different calorimeters finally provides data between 10(-3) Hz and 10(6) Hz. In this frequency range the dynamic glass transition shifts about 120 K.

In situ investigation of vapor-deposited glasses of toluene and ethylbenzene via alternating current chip-nanocalorimetry.

Vapor-deposited glasses of toluene and ethylbenzene have been characterized by in situ ac chip-nanocalorimetry. The high sensitivity of this method allows the detection of small changes in the heat capacity of nanogram size samples. We observe that vapor-deposited glasses have up to 4% lower heat capacities than the ordinary glass. The largest heat capacity decrease and the most kinetically stable glasses of toluene and ethylbenzene are observed in a range of deposition temperatures between 0.75 T(g) and 0.96 T(g). Compared to larger molecules, deposition rate has a minor influence on the kinetic stability of these glasses. For both toluene and ethylbenzene, the kinetic stability is strongly correlated with the heat capacity decrease for deposition temperatures above 0.8 T(g). In addition, ac-nanocalorimetry was used to follow the isothermal transformation of the stable glasses into the supercooled liquid at temperatures slightly above T(g). Toluene and ethylbenzene stable glasses exhibit a constant transformation rate which is consistent with the growth front mechanism recently demonstrated for tris-naphthylbenzene and indomethacin. The kinetic stability of the most stable toluene and ethylbenzene glasses is comparable to that observed for other stable glasses formed by vapor deposition.

Differential alternating current chip calorimeter for in situ investigation of vapor-deposited thin films.

Physical vapor deposition can be used to produce thin films with interesting material properties including extraordinarily stable organic glasses. We describe an ac chip calorimeter for in situ heat capacity measurements of as-deposited nanometer thin films of organic glass formers. The calorimetric system is based on a differential ac chip calorimeter which is placed in the vacuum chamber for physical vapor deposition. The sample is directly deposited onto one calorimetric chip sensor while the other sensor is protected against deposition. The device and the temperature calibration procedure are described. The latter makes use of the phase transitions of cyclopentane and the frequency dependence of the dynamic glass transition of toluene and ethylbenzene. Sample thickness determination is based on a finite element modeling of the sensor sample arrangement. In the modeling, a layer of toluene was added to the sample sensor and its thickness was varied in an iterative way until the model fit the experimental data.

Origin of glassy dynamics in a liquid crystal studied by broadband dielectric and specific heat spectroscopy.

A combination of broadband dielectric (10{-2}Hz-10{9}Hz) and specific heat (10{-3}Hz-2 x 10{3}Hz) spectroscopy is employed to study the molecular dynamics of the glass-forming nematic liquid crystal E7 in a wide temperature range. In the region of the nematic phase the dielectric spectra show two relaxation processes which are expected theoretically: the delta relaxation which corresponds to rotational fluctuations of the molecules around its short axis and the tumbling mode at higher frequencies than the former one. For both processes the temperature dependence of the relaxation rates follows the Vogel-Fulcher-Tammann formula which is characteristic for glassy dynamics. By applying a detailed data analysis, it is shown that close to the glass transition the tumbling mode has a much steeper temperature dependence than the delta process. The former has a Vogel temperature which is by 30K higher than that of the delta relaxation. Specific heat spectroscopy gives one relaxation process in its temperature and frequency dependence which has to be assigned to the alpha relaxation (dynamic glass transition). The unique and detailed comparison of the temperature dependence of the dielectric and the thermal relaxation rates delivers unambiguously that the dielectric tumbling mode has to be related to the dynamic glass transition.

Pattern formation in thin polystyrene films induced by an enhanced mobility in ambient air.

Thin polystyrene films (prepared in a sandwich geometry between two aluminum electrodes) develop a characteristic pattern in ambient air when kept above the glass-transition temperature, whereas they remain unchanged in vacuum or in a pure nitrogen atmosphere. Measurements by broadband dielectric spectroscopy, capacitive dilatometry, and AC calorimetry reveal that the pattern formation is initiated in ambient air by an increase in the average relaxation rate of the dynamic glass transition, which results in a corresponding reduction of the glass-transition temperature. Infrared measurements evidence that this is caused by a shift of the molecular weight distribution to lower values as a consequence of oxygen-induced chain scissions.

Molecular dynamics of hyperbranched polyesters in the confinement of thin films.

Broadband Dielectric Spectroscopy is employed to investigate the molecular dynamics in thin films of hyperbranched polyesters (type AB(1)B(2), with -OH and -OCOCH(3) as terminal groups). Three relaxation processes are detected: alpha, beta and gamma. While the latter two are not influenced by the confinement, a pronounced effect is observed on the alpha relaxation: with decreasing film thickness the slower relaxation modes of the dynamic glass transition are gradually suppressed, resulting in an increase of the average relaxation rate and in a linear decrease of the dielectric strength. This is attributed to an immobilization in confinement of the polymeric segments located at the periphery of the hyperbranched macromolecular structures.

The synthesis of 15N- and deuterium-substituted, spin-labeled analogues of NAD+ and their use in EPR studies of dehydrogenases.

Two spin-labeled analogues of NAD+ were synthesized with an 15N and perdeuterated nitroxide radical, 4-amino-2,2,6,6-[2H17, 15N]tetramethylpiperidone-1-oxyl, which was attached to either the C-6 or C-8 position of the purine ring. The EPR spectra of these derivatives exhibit an approx. 6-fold increase in sensitivity compared with the corresponding 14N, protonated analogues due to a decrease in both the number of nuclear manifolds (from three to two) and the linewidth. The enhanced spectral resolution obtained with (2H17, 15N)spin-labeled-NAD+ analogues has facilitated simulation of the EPR lineshape of the nucleotide bound to lactate dehydrogenase (L-lactate:NAD+ oxidoreductase, EC 1.1.1.27). The spin-label moiety exhibits highly constrained motion indicative of a single environment. The motion of the spin label does not reflect the overall motion of the enzyme; rather, it is characteristic of some limited mobility relative to the lactate dehydrogenase. By contrast, the spin label on the membrane-bound enzyme, D-beta-hydroxybutyrate dehydrogenase (D-beta-hydroxybutyrate:NAD+ oxidoreductase, EC 1.1.1.30), is completely immobilized and exhibits two distinct spectral components for spin-labeled NAD+, which appear to differ in the polarity of the environment of the nitroxide.

[Anti-epileptic agents during pregnancy. A prospective study on the course of pregnancy, malformations and child development]. / Antiepileptika während der Schwangerschaft. Eine prospektive Studie über Schwangerschaftsverlauf, Fehlbildungen und kindliche Entwicklung.

In a prospective controlled study 70 children of females with epilepsy and on anticonvulsant medication during pregnancy were investigated. It was shown that epileptic females had stillbirths more frequently than expected. After delivery particularly children on phenobarbitone are sedated. Due to weak suckling this may lead to inadequate food intake. Withdrawal symptoms manifest in affected children as hyperexcitability lasting for weeks. Children of epileptic women on medication are generally smaller, of lower weight and have smaller heads than children from all control groups. Ingestion of more than one anticonvulsant leads to an even more pronounced reduction of infantile body measurements below the expected mean value. Small malformations are observed more frequently after intrauterine exposition to anticonvulsants than in the control groups. Ingestion of more than one anticonvulsant leads to an increase of the number of small malformations in the child than after single drug therapy. Children of epileptic parents are affected more frequently by large malformations than children of nonepileptic parents.

[Experiences with the Rostock artificial heart]. / Erfahrungen mit dem Rostocker künstlichen Herz.

A totally artificial heart--the Rostock totally artificial heart (Rostock TAH) was implanted in calves. We can give the following deductions after 27 examinations: -- The Rostock TAH was tested successfully in endurance test about 7 months; it show no sign of wear. -- The surgical technique of the implantation was standardised and a successful experimentation is possible. -- The longest survival time was 15 days. The hemodynamic early results were very good in 3 other animals. -- Modifications of the Rostock TAH were taken up relating to the dimensions of the artificial ventriculi and by mounting a screw cap for avoiding an air embolism. -- Adaption tests in the corpse show that the present form of the artificial heart is not ideal for a possible application in man. -- The problem is still existing in developing a suitable drive system locates intrathoracically. The present drive and control system on a pneumatic base is qualified only for the animal experiment but not for a possible application in man.

Characterization of the receptor subtype involved in alpha-adrenoceptor-mediated modulation of serotonin release from rat brain cortex slices.

Rat brain cortex slices preincubated with 3H-5-hydroxytryptamine and superfused with physiological salt solution were stimulated electrically at a frequency of 3 Hz. 1. The electrically evoked 3H-overflow was decreased by clonidine, noradrenaline and B-HT 920 in a concentration-dependent manner (negative logarithms of the IC30 values: 6.66, 6.55 and 4.40, respectively) 2. Phenylephrine 10-5 M (which increased basal 3H-efflux) and methoxamine 10-4 M decreased the impulse-evoked 3H-overflow by less than 25% whereas lower concentrations were ineffective. 3. Yohimbine produced a shift to the right of the concentration-response curves of noradrenaline (apparent pA2: 6.93) and clonidine (apparent pA2: 7.06) for their inhibitory effects on evoked 3H-overflow. Rauwolscine also shifted the concentration-response curve of noradrenaline to the right (apparent pA2: 7.29), whereas prazosin (10-6 and 3.2 x 10-6 M) was ineffective in this respect. These results suggest that the alpha-adrenoceptors on the serotoninergic nerve fibres belong to the alpha2-subtype.

Semi-reversible cross-linking. Synthesis and application of a novel heterobifunctional reagent.

The synthesis of a novel heterobifunctional cross-linking reagent, 3-(4-azido-2-nitrobenzoylseleno)propionic acid is described. The selenol ester function serves as a selective and reversible thiol reagent. Cross-linking is carried out photochemically via nitrene generation. The reagent is well suited for the identification of the environment of a defined cysteine residue according to the principle of semi-reversible cross-linking (Trommer, W.E., Friebel, K., Kiltz, H.-H. & Kolkenbrock. H. (1977) Adv. Exp. Med. Biol. 86A, 187-195). Cleavage of the thiol ester bond (the first anchor point) can be achieved by a variety of labels carrying an amino function thus giving rise to labelled amino acids or proteins in a distance of about 0.7 nm from the known cysteine residue. Optimal conditions were determined by reaction of 3-(4-azido-2-nitrobenzoylseleno)propionic acid and of its unsubstituted analog with glutathione and N alpha-benzoylglycyllysine. Nucleosidetriphosphate-adenylate kinase from pig muscle was chosen as an example to demonstrate the usefulness of the reagent. 14C-labelled aminobutyric acid was applied to cleave the thiol ester bond between the reagent and cysteine-25 leading to labelling of the N-terminal arginine peptide.

Alpha-adrenoceptor-mediated modulation of 5-hydroxytryptamine release from rat brain cortex slices.

Slices of rat brain cortex preincubated with 3H-5-hydroxytryptamine were superfused with physiological salt solution and stimulated electrically, or they were superfused with Ca2+-free solution containing 25 mM K+ and stimulated by introduction of 1.3 mM CaCl2 for 2 min. 1. The electrically evoked 3H overflow was decreased by noradrenaline and increased by phentolamine in a concentration-dependent manner. 2. Phentolamine caused a parallel shift to the right of the concentration-response curve of noradrenaline for its inhibitory effect on impulse-evoked 3H overflow; by contrast, it left the inhibitory effect of unlabelled 5-hydroxytryptamine on the electrically evoked 3H overflow unaffected. 3. Propranolol did not alter the inhibitory effect of noradrenaline on impulse-induced 3H overflow. 4. The increasing effect of phentolamine on the electrically evoked 3H overflow was not modified by paroxetine. 5. Cocaine (at a concentration which almost completely blocks the uptake of 3H-noradrenaline but only partially that of 3H-5-hydroxytryptamine into cortex slices) decreased impulse-evoked 3H overflow. This effect was abolished by phentolamine. 6. In the presence of tetrodotoxin throughout superfusion, the Ca2+-evoked 3H-overflow from slices superfused with Ca2+-free solution was inhibited by noradrenaline and increased by phentolamine. These findings suggest that the terminal serotoninergic fibers of rat brain cortex possess alpha-adrenoceptors, activation of which by exogenous or endogenous noradrenaline leads to inhibition of the release of 5-hydroxytryptamine.

The nature of the substrate inhibition in lactate dehydrogenases as studied by a spin-labeled derivative of NAD.

The formation of the ternary complex of lactate dehydrogenase (L-lactate:NAD+ oxidoreductase, EC 1.1.1.27) from pig heart and skeletal muscle with the adduct of pyruvate to NAD", spin-labeled at N6 was studied by ultraviolet spectroscopy and ESR techniques. According to ultraviolet measurements we found identical binding characteristics for the natural coenzyme and its spin-labeled analog. The rate by which the ESR signal of free spin-labeled NAD+ decreased upon addition of pyruvate to the binary complexes was substantially different in the two isozymes. With the heart type an initial drop followed by a further linear decrease, zero order in the enzyme and coenzyme concentration was observed. In case of the skeletal muscle isozyme no immediate reaction and a first order process occurred. The initial reaction can be attributed to a non-covalent enzyme/spin-labeled NAD+/pyruvate complex with a dissociation constant for pyruvate of 11 +/- 1 mM, thus explaining the well-known substrate inhibition in the heart isozyme above 2 mM pyruvate. The further reaction is then determined by the buffer dependent enolization of pyruvate. In the muscle isozyme formation of the covalent adduct is not assisted by prior binding of pyruvate in a non-covalent ternary complex and therefore the rate depends on the binary complex concentration.

Relations between embedded figures test performance and dimensions of the I-E scale.

Relations between an embedded figures measure of field independence and various dimensions of Rotter's internal-external locus of control scale were investigated. The general absence of significant correlations suggests that these variables are essentially unrelated.

Simple parabiotic chamber for the study of microorganisms in organ culture.

A simple parabiotic chamber which is easy to manipulate, does not leak, allows microscopic examination of organ cultures, and is easy to sterilize is described.