Synthesis of [4,5-Bis(hydroxymethyl)-1,3-dioxolan-2-yl]nucleosides as Potential Inhibitors of HIV

The synthesis of 1,3-dioxolan-2-ylnucleosides and related chemistry is described. We have shown that 2-methoxy-1,3-dioxolane (6) reacts with silylated thymine and trimethylsilyl triflate to give the acyclic formate ester 1-[2-(formyloxy)ethyl]thymine (8) rather than 1-(1,3-dioxolan-2-yl)thymine (7). A tentative mechanism which could explain this result is discussed. On the other hand, 2-methoxy-1,3-dioxolane 13c reacts with silylated bases to give [4,5-bis(hydroxymethyl)-1,3-dioxolan-2-yl]nucleosides, thus representing the first examples of this novel class of compounds. The nature of the nucleobase and the hydroxyl protecting groups was found to have great influence on the reaction and on the stability of the nucleosides. Compounds 16 and 18 were found to be inactive when tested for anti HIV-1 activity in vitro.     

Fish freshness detection by a computer screen photoassisted based gas sensor array

In the last years a large number of different measurement methodologies were applied to measure the freshness of fishes. Among them the connection between freshness and headspace composition has been considered by gas chromatographic analysis and from the last two decades by a number of sensors and biosensors aimed at measuring some characteristic indicators (usually amines). More recently also the so-called artificial olfaction systems gathering together many non-specific sensors have shown a certain capability to transduce the global composition of the fish headspace capturing the differences between fresh and spoiled products. One of the main objectives related to the introduction of sensor systems with respect to the analytical methods is the claimed possibility to distribute the freshness control since sensors are expected to be “portable” and “simple”. In spite of these objectives, until now sensor systems did not result in any tool that may be broadly distributed. In this paper, we present a chemical sensor array where the optical features of layers of chemicals, sensitive to volatile compounds typical of spoilage processes in fish, are interrogated by a very simple platform based on a computer screen and a web cam. An array of metalloporphyrins is here used to classify fillets of thawed fishes according to their storage days and to monitor the spoilage in filleted anchovies for a time of 8 h. Results indicate a complete identification of the storage days of thawed fillets and a determination of the storage time of anchovies held at room temperature with a root mean square error of validation of about 30 min.The optical system produces a sort of spectral fingerprint containing information about both the absorbance and the emission of the sensitive layer. The system here illustrated, based on computer peripherals, can be easily scaled to any device endowed with a programmable screen and a camera such as cellular phones offering for the first time the possibility to fulfil the sensor expectation of diffused and efficient analytical capabilities.     

Synthesis of Novel Isothionucleosides as Potential Antiviral Agents

The synthesis of novel isothionucleosides is described. The thioether moiety was prepared via a highly regioselective opening of chiral thiirane 9 with vinylmagnesium bromide.     

The on–off network traffic model under intermediate scaling

The result provided in this paper helps complete a unified picture of the scaling behavior in heavy-tailed stochastic models for transmission of packet traffic on high-speed communication links. Popular models include infinite source Poisson models, models based on aggregated renewal sequences, and models built from aggregated on–off sources. The versions of these models with finite variance transmission rate share the following pattern: if the sources connect at a fast rate over time the cumulative statistical fluctuations are fractional Brownian motion, if the connection rate is slow the traffic fluctuations are described by a stable Lévy motion, while the limiting fluctuations for the intermediate scaling regime are given by fractional Poisson motion. In this paper, we prove an invariance principle for the normalized cumulative workload of a network with m on–off sources and time rescaled by a factor a. When both the number of sources m and the time scale a tend to infinity with a relative growth given by the so-called ’intermediate connection rate’ condition, the limit process is the fractional Poisson motion. The proof is based on a coupling between the on–off model and the renewal type model.     

Direct quantitative evaluation of complex substances using computer screen photo-assisted technology: the case of red wine

The combination of computer monitors and webcams has been recently demonstrated to behave as a sort of spectrophotometer able to classify and recognize substances according to their light absorption and emission properties. This measurement technique is known as computer screen photoassisted technique (CSPT).In this paper, it is demonstrated for the first time and in the case of a complex sample such as red wine, that also quantification of integral parameters (colour indicators) and specific compounds (total anthocyanins and polyphenols) is possible through a multivariate analysis of CSPT fingerprints. Most of the properties of the method are due to the combination of light emission and absorption properties that are captured by the CSPT platform. Thanks to this combination, a CSPT fingerprint may contain a comparable amount of information with respect to standard spectrophotometers.Wine measurements were performed on intact samples without the intervention of chemical mediators. The regression models, built by Partial Least Squares, obtained errors of estimation of colour parameters, total polyphenols and anthocyanines that are comparable with those typical of the standard methods in use.Since computation functionalities, video capture and display are embedded in a steadily growing number of ubiquitously distributed equipments (from portable computers to cellular phones), these results indicate a viable methodology for low-cost and largely diffused analytical capabilities.     

Coulomb scattering in the eikonal approximation

We derive a new expression for the eikonal approximation of the nuclear Coulomb scattering amplitude. Our expression should be particularly useful for the treatment of Coulomb scattering in hadron-nucleus and nucleus-nucleus scattering at high and intermediate energies.     

Porphyrin-doped solgel-lined structured optical fibers for local and remote sensing

We constructed a type of sensor by depositing a solgel layer within the interior holes of a silica-structured fiber and, subsequently, coating this with an acid-responsive porphyrin. Protonation of the porphyrin by an acidic gas (HCl in this case), is detected by a large change in the visible spectrum. Compared to previous work on a liquid-core sensor in a structured optical fiber, the signal-to-noise ratio of this gas sensor shows a reduced signal strength, but the detection rate is increased about fortyfold.     

De novo sequencing of proteolytic peptides by a combination of C-terminal derivatization and nano-electrospray/ collision-induced dissociation mass spectrometry

A series of synthetic peptides (3-15 residues), C-terminally derivatized with 4-aminonaphthalenesulfonic acid (ansa), have been analyzed on a hybrid magnetic sector-orthogonal acceleration time-of-flight tandem mass spectrometer, fitted with a nano-electrospray (nano-ES) interface. Deprotonated molecules generated by negative-ion ES were subjected to collision-induced dissociation (CID) using either methane or xenon as the collision gas, at a collision energy of 400 eV (laboratory frame of reference). As a consequence of charge localization on the sulfonate group, only C-terminal fragment ions were formed, presumably by charge-remote fragmentation mechanisms. Interpretable CID spectra were obtained from fmol amounts of the small peptides (up to 6 residues), whereas low pmol amounts were required for the larger peptides. CID spectra were also recorded of derivatized, previously noncharacterised peptides obtained by proteolysis of cytosolic hamster liver aldehyde dehydrogenase. Interpretation of these CID spectra was based on rules established for the fragmentation of the synthetic peptides. This study shows that derivatization with ansa may be useful in the de novo sequencing of peptides.