Ice nucleation on BaF2(111)

The mechanism of heterogeneous ice nucleation on inorganic substrates is not well understood despite work on AgI and other materials over the past 50 years. We have selected BaF(2) as a model substrate for study since its (111) surface makes a near perfect match with the lattice of the basal face of I(h) ice and would appear to be an ideal nucleating agent. Two series of experiments were undertaken. In one, nucleation of thin film water formed from deposition of vapor on BaF(2)(111) faces was explored with the finding that supercooling to -30 degrees C was required before freezing occurred. In the other series, nucleation of liquid water on submerged BaF(2) crystals was studied. Here supercooling to -15 degrees C was needed before ice formed. The reason why BaF(2) is such a poor nucleating agent contains clues to realistic mechanisms of heterogeneous nucleation. Our explanation of these results follows the model of Fletcher [J. Chem. Phys. 29, 572 (1958)] who showed that heterogeneous ice nucleating ability depends on how well ice wets a substrate. In this view, a smooth BaF(2)(111) face is poor at nucleation because ice only partially wets its surface. In an extension of Fletcher's model, our calculations, consistent with the experimental results demonstrate that the pitting of a submerged BaF(2) crystal dramatically improves its ice nucleating ability.     

13C substituent effects in monosubstituted benzenes

A brief analysis is presnted of the current understanding of substituent perturbations in monosubstituted benzenes as determined by substituent induced carbon chemical shifts. A critical tabulation of the four substituent chemical shifts is given for c. 700 monosubstituted benzenes.     

A laser extinction based sensor for simultaneous droplet size and vapor measurement

Multiphase flows involving liquid droplets in association with gas flow occur in many industrial and scientific applications. Recent work has demonstrated the feasibility of using optical techniques based on laser extinction to simultaneously measure vapor concentration and temperature and droplet size and loading. This work introduces the theoretical background for the optimal design of such laser extinction techniques, termed WMLE (wavelength-multiplexed laser extinction). This paper focuses on the development of WMLE and presents a systematic methodology to guide the selection of suitable wavelengths and optimize the performance of WMLE for specific applications. WMLE utilizing wavelengths from 0.5 to 10 μm is illustrated for droplet size and vapor concentration measurements in an example of water spray, and is found to enable unique and sensitive Sauter mean diameter measurement in the range of ～1–15 μm along with accurate vapor detection. A vapor detection strategy based on differential absorption is developed to extend accurate measurement to a significantly wider range of droplet loading and vapor concentration as compared to strategies based on direct fixed-wavelength absorption. Expected performance of the sensor is modeled for an evaporating spray. This work is expected to lay the groundwork for implementing optical sensors based on WMLE in a variety of research and industrial applications involving multi-phase flows.     

Analytical approaches to investigate transmitter content and release from single secretory vesicles

The vesicle serves as the primary intracellular unit for the highly efficient storage and release of chemical messengers triggered during signaling processes in the nervous system. This review highlights conventional and emerging analytical methods that have used microscopy, electrochemistry, and spectroscopy to resolve the location, time course, and quantal content characteristics of neurotransmitter release. Particular focus is on the investigation of the synaptic vesicle and its involvement in the fundamental molecular mechanisms of cell communication.     

Zur Bestimmung des Salizyls?uremethylesters

Ohne Zusammenfassung     

Vesicular release dynamics are altered by the interaction between the chemical cargo and vesicle membrane lipids

The release of the cargo from soft vesicles, an essential process for chemical delivery, is mediated by multiple factors. Among them, the regulation by the interaction between the chemical cargo species and the vesicular membrane, widely existing in all vesicles, has not been investigated to date. Yet, these interactions hold the potential to complicate the release process. We used liposomes loaded with different monoamines, dopamine (DA) and serotonin (5-HT), to simulate vesicular release and to monitor the dynamics of chemical release from isolated vesicles during vesicle impact electrochemical cytometry (VIEC). The release of DA from liposomes presents a longer release time compared to 5-HT. Modelling the release time showed that DA filled vesicles had a higher percentage of events where the time for the peak fall was better fit to a double exponential (DblExp) decay function, suggesting multiple kinetic steps in the release. By fitting to a desorption–release model, where the transmitters adsorbed to the vesicle membrane, the dissociation rates of DA and 5-HT from the liposome membrane were estimated. DA has a lower desorption rate constant, which leads to slower DA release than that observed for 5-HT, whereas there is little difference in pore size. The alteration of vesicular release dynamics due to the interaction between the chemical cargo and vesicle membrane lipids provides an important mechanism to regulate vesicular release in chemical and physiological processes. It is highly possible that this introduces a fundamental chemical regulation difference between transmitters during exocytosis.

The release of the cargo from soft vesicles, an essential process for chemical delivery, is mediated by multiple factors.     

Dimroth-type rearrangement of 1-benzyl- and 1-glycosyl-5-aminoimidazoles to 4-(N-substituted amino)imidazoles

An efficient route is described to an unusual exocyclic 4-β-d-ribofuranosyl-aminoimidazole nucleoside, related 4-N-benzylaminoimidazoles and imidazole analogues of precursors in the de novo biosynthesis of purines, via a regiospecific and stereoselective base-catalysed Dimroth-type rearrangement of 1-ribofuranosyl and 1-benzyl-5-aminoimidazoles. Use of a ¹⁵N labelled precursor showed the unequivocal endo- to exocyclic translocation of the nitrogen atom during the rearrangement.