The acid-catalysed reaction of thiols with alkyl 2,3-dideoxy-glyc-2-enopyranosides or glycals

The acid-catalysed (HCl or SnCl₄) reaction of alkyl 2,3 dideoxy-glyc-2-enopyranosides or 3,4,6-tri-O-acetyl-D-glycals with thiols leads to mixtures of alkyl 2,3-dideoxy-1-thio-glyc-2-enopyranosides and 3-S-alkyl-3-thioglycals. Under equilibrium conditions the latter are the preponderant products of the reaction. Cross experiments have confirmed the intermediacy of the allylic carbocation in the reaction. A rationalization of the substitution reactions of 1,2- and 2,3-unsaturated sugars based on HSAB principle has been proposed.     

Some Results Connected with the Class Number Problem in Real Quadratic Fields

We investigate arithmetic properties of certain subsets of square-free positive integers and obtain in this way some results concerning the class number h（d） of the real quadratic field Q（√d）. In particular, we give a new proof of the result of Hasse, asserting that in this case h（d） = 1 is possible only if d is of the form p, 2q or qr. where p.q. r are primes and q≡r≡3（mod 4）.     

Heats of displacement of hydrogen from palladium by noble gases

It has been observed that noble gases, such as helium, neon and argon produce heat evolution when contacted with Pd powder partially saturated with hydrogen. These phenomena have been studied with flow-through adsorption microcalorimetry. The observed exothermic effects are comparable to those usually associated with the heat of sorption of hydrogen in palladium. It is suggested that the noble gases displace the adsorbed H species from the surface of Pd, causing their reabsorption in the Pd lattice with the exothermic heat of PdH bonds formation, or the formation of H₂, both heat evolutions being observed with a flow-through microcalorimeter.     

Mechanisms of modulation gap detection

It has been postulated that the central auditory system contains an array of modulation filters, each responsive to a different range of modulation frequencies present at the outputs of the (peripheral) auditory filters. In the present experiments, we tested what we call the "dip hypothesis," that a gap in modulation is detected using the "dip" in the output of the modulation filter tuned to the modulator frequency. In experiment 1, the task was to detect a gap in the sinusoidal amplitude modulation imposed on a 4-kHz carrier. The modulator preceding the gap ended with a positive-going zero-crossing. There were three conditions, differing in the phase at which the modulator started at the end of the gap; zero-phase, at a positive-going zero-crossing; pi-phase, at a negative-going zero-crossing; and "preserved" phase, at the phase the modulator would have had if it had continued without interruption. Modulation frequencies were 5, 10, 20, and 40 Hz. Psychometric functions for detection of the gap were measured using a two-alternative forced-choice task. For the zero-phase and preserved-phase conditions, the detectability index, d', increased monotonically with increasing gap duration. For the pi-phase condition, performance was good (d' > 1) for small gap durations, and initially worsened with increasing gap duration, before improving again for longer gap durations. This is the pattern of results expected from the dip hypothesis, provided that the modulation filters have Q values of 2 or more. However, it is also possible that a rhythm cue was used to improve performance in the pi-phase condition for short gap durations; the introduction of the gap markedly disrupted the regular rhythm produced by the modulator peaks. In experiment 2, the rhythm cue was disrupted by varying the modulator period randomly around its nominal value, except for the modulator periods immediately before and after the gap. This markedly impaired performance, and resulted in psychometric functions that were very similar for the zero-phase and pi-phase conditions. This pattern of results is inconsistent with the dip hypothesis. For both experiments, modulation gap "thresholds" (d' approximately 1) were roughly constant when expressed as a proportion of the modulator period. Possible mechanisms of modulation gap detection are discussed and evaluated.     

Behaviour of copper(II) and nickel(II) dialkyldithiocarbamates on polar and non-polar stationary phases

Summary Fifteen Dialkyldithiocarbamate complexes each of copper(II) and Ni(II) have been prepared and the retention times of these complexes have been measured on the non-polar OV-101 phase and the polar NGA and OV-225 phases. The relationship has been studied between the retention characteristics of the complexes and their structure. The lenght of the alkyl substituent, regarded as a steric hindrance, turned out to affect the retention of the complexes on the non-polar phases.

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Verhalten von Kupfer(II)- und Nickel(II)-dialkyldithiocarbamaten auf polaren und unpolaren stationären Phasen

Zusammenfassung Je 15 Dialkyldithiocarbamatkomplexe von Kupfer(II) und Nickel(II) wurden dargestellt und ihre Retentionszeiten auf der unpolaren Phase OV-101 sowie den polaren Phasen NGA und OV-225 gemessen. Die Beziehung zwischen der Retentionscharakteristik der Komplexe und ihrer Struktur wurde untersucht. Es zeigte sich, daß die Länge des Alkylsubstituenten (als sterische Hinderung) die Retention auf der unpolaren Phase beeinträchtigt.

     

Interferometric technique for measuring broadband ultrashort pulses at the sampling limit

We present a new technique for measuring ultrashort optical pulses by use of spectral phase interferometry for direct electric-field reconstruction that is suitable for large bandwidth pulses. The method does not require generation of a replica of the pulse to be measured and encodes the spectral phase information in a spatial interference pattern. A major advantage of this method is that the spectral sampling saturates the Whittaker-Shannon bound. Moreover, the technique allows for the characterization of some types of space-time coupling. An experimental demonstration of the technique is presented.     

Structural analysis and molecular modelling of the Cu/Zn-SOD from fungal strain Humicola lutea 103

The native form of Cu/Zn-superoxide dismutase, isolated from fungal strain Humicola lutea 103 is a homodimer that coordinates one Cu(2+) and one Zn(2+) per monomer. Cu(2+) and Zn(2+) ions play crucial roles in enzyme activity and structural stability, respectively. It was established that HLSOD shows high pH and temperature stability. Thermostability of the glycosylated enzyme Cu/Zn-SOD, isolated from fungal strain H. lutea 103, was determined by CD spectroscopy. Determination of reversibility toward thermal denaturation for HLSOD allowed several thermodynamic parameters to be calculated. In this communication we report the conditions under which reversible denaturation of HLSOD exists. The narrow range over which the system is reversible has been determined using the strongest test of two important thermodynamic independent variables (T and pH). Combining both these variables, the "phase diagram" was determined, as a result of which the real thermodynamic parameters (ΔC(p), ΔH(exp)°, and ΔG(exp)°) was established. Because very narrow pH-interval of transitions we assume they are as result of overlapping of two simple transitions. It was found that ΔH(o) is independent from pH with a value of 1.3 kcal/mol and 2.8 kcal/mol for the first and the second transition, respectively. ΔG(o) was pH-dependent in all studied pH-interval. This means that the transitions are entropically driven, these. Based on this, these processes can be described as hydrophobic rearrangement of the quaternary structure. It was also found that glycosylation does not influence the stability of the enzyme because the carbohydrate chain is exposed on the surface of the molecule.