Non-covalent assembly of a photoswitchable surface

A noncovalently bound multilayered thin film in which individual layers are linked by metal ligand interactions undergoes a photochemically initiated permanent change in surface wettability. The film consists of three separate layers: a SAM on gold of 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid, a layer of Cu(II) ions that are deposited onto the SAM and bind symmetrically in the site provided by the two carboxylate groups and the pyridyl nitrogen atom, and a layer of cis-2,2'-dipyridylethylene, which caps the Cu(II) layer by complexation through both pyridyl nitrogen atoms (Film I). Photoexcitation of the film in chloroform at 300 nm leads to substantial cis-trans isomerization as indicated by conductivity, impedance, grazing incidence IR, and contact angle measurements. The latter show a decrease in contact angle (increase in wettability) of 17 degrees , which is attributed to exposure of both the underlying Cu(II) layer and one of the pyridyl ring nitrogen atoms following isomerization to the trans isomer.     

On a conjecture of Whittaker concerning uniformization of hyperelliptic curves

This article concerns an old conjecture due to E. T. Whittaker, aiming to describe the group uniformizing an arbitrary hyperelliptic Riemann surface as an index two subgroup of the monodromy group of an explicit second order linear differential equation with singularities at the values .

Whittaker and collaborators in the thirties, and R. Rankin some twenty years later, were able to prove the conjecture for several families of hyperelliptic surfaces, characterized by the fact that they admit a large group of symmetries. However, general results of the analytic theory of moduli of Riemann surfaces, developed later, imply that Whittaker's conjecture cannot be true in its full generality.

Recently, numerical computations have shown that Whittaker's prediction is incorrect for random surfaces, and in fact it has been conjectured that it only holds for the known cases of surfaces with a large group of automorphisms.

The main goal of this paper is to prove that having many automorphisms is not a necessary condition for a surface to satisfy Whittaker's conjecture.

     

MRI characterization of residual mediastinal masses in Hodgkin's disease: long-term follow-up

Our purpose was to evaluate the role of MRI in distinguishing fibrous from active residual masses in treated Hodgkin's disease. Forty patients with residual mediastinal mass larger than 1.5 cm underwent MRI 1, 3, 6, and 12 months after the end of cycles of prescribed chemotherapy or combined chemoradiotherapy. The MRI examinations were performed on a 0.5 and a 1.5 T systems, using T(1) before and after gadolinium injection and T(2)-weighted sequences. Each time the residual mass was evaluated in size and signal intensity on spin echo (SE) T(2)-weighted images and on SE T(1)-weighted images after contrast medium. Low signal intensity and low contrast enhancement were considered signs of inactive residues; homogeneous high signal intensity and high contrast enhancement were indicative of active residual disease; heterogeneous signal intensity and heterogeneous contrast enhancement were indicative of partial remission or necrotic/inflammatory phenomena. MR showed high diagnostic accuracy in the evaluation of Hodgkin's mediastinal residues after treatment, if performed at least 6 months after the end of therapy, reaching the highest sensitivity and specificity values at 12 month follow-up (considering the three parameters-T(2) signal intensity, contrast-enhancement, and size-all together). If we consider the single parameters individually, we can observe that size variation remains the more valuable parameter to predict or to exclude a relapse. MR diagnostic accuracy at the 6-month follow-up was lower due to the higher incidence of inhomogeneous pattern. The accuracy of MR performed at 1 and at 3 months after the end of therapy was not satisfying. This represents a clinical problem because the most important clinical decisions have to be taken just in this early post-treatment phase.     

ATR/FTIR characterization of Steinernema glaseri and Heterorhabditis indica

The use of Fourier transform mid-infrared spectroscopy with attenuated total reflection for characterizing entomopathogenic nematodes is evaluated for the first time. The resulting spectra of Steinernema glaseri and Heterorhabditis indica were compared with the spectrum of Caenorhabditis elegans. In the absorption spectra generated by the nematodes samples, the absorption bands were assigned to the molecular species and some important components were identified including triglycerides, trehalose, glycogen and collagen. Also, the use of star diagrams for the fingerprint section of nematode spectra for separating genera is discussed.     

A new algorithm for NMR spectral normalization.

There is increasing use of high-resolution NMR spectroscopy to examine variations in cell metabolism and/or structure in response to numerous physical, chemical, and biological agents. In these types of studies, in order to obtain relative quantitative information, a comparison between signal intensities of control samples and treated or exposed ones is often conducted. The methods thus far developed for this purpose are not directly related to the overall intrinsic properties of the samples, but rather to the addition of external substances of known concentrations or to indirect measurement of internal substances. In this paper, a new method for quantitatively comparing the spectra of cell samples is presented. It depends on a normalization algorithm which takes into consideration all cell metabolites present in the sample. In particular, the algorithm is based on maximizing, by an opportune sign variable measure, the spectral region in which the two spectra are superimposed. The algorithm was tested by Monte Carlo simulations as well as experimentally by comparing two samples of known contents with the new method and with an older method using a standard. At the end, the algorithm was applied to real spectra of cell samples to show how it could be used to obtain qualitative and quantitative biological information.     

NMR analysis of multiple samples using parallel coils: improved performance using reference deconvolution and multidimensional methods

Improvements in the Multiplex Sample NMR method are investigated to explore its capabilities of analyzing multiple samples simultaneously. Issues of quantitation and resolution in the multiple-coil probe are examined in one- and two-dimensional experiments. Improvements in quantitation are shown to result from the use of reference deconvolution for one-dimensional experiments, while the use of two-dimensional methods has much improved resolution and shows the potential for significantly increased parallelism. A multiplicative scheme is shown to be an easily implemented, effective method for generating individual sub-spectra from individual samples.     

Weyl formula for multi-quasi-elliptic operators. of Schrödinger type

In this work we consider a general class of Schr?dinger type operators, associated with multi-quasi-elliptic symbols. We give a precise estimate of the remainder of the so-called Weyl asymptotic formula for the eigenvalues of these operators. In order to reach our aim, we use the Weyl–H?rmander calculus, with locally temperate metrics and weights, and interpolation techniques. Received: February 14, 2000; in final form: October 29, 2000?Published online: July 13, 2001     

Lingshuine,an Unexpected Passerini Product from the Hainan Sponge Axinyssa variabilis

Lingshuine ( 1 ), a novel sesquiterpene amide, along with three known N‐containing compounds, 2 – 4 , have been isolated from the Hainan sponge Axinyssa variabilis. The structure of 1 was elucidated by detailed analysis of the spectroscopic data and by chemical methods. Lingshuine represents the first example of a Passerini product formed during the isolation process.     

Thermo gravimetric analysis of supramolecular complexes of p-tert-butylcalix[6]arene and ammonium cations: crystal structure of diethylammonium complex

Thermo gravimetric analysis of ammonium-p-tert-butylcalix[6]arene salts were carried out to determine the stoichiometry of the inclusion compounds and the temperature of leaving of the ammonium cation, as amine, from the solid phase by a reverse proton transfer reaction to calixarene. The chain length of the amine molecules and their relative basicity order are the main factors which determine the decomplexation temperatures for the ammonium salts of piperidinium, diethylammonium, ethylenediammonium, morpholinium, s-butylammonium, butylammonium, hexylammonium and triethylammonium salts of p-tert-butylcalix[6]arene anion. The solid state structure of bis-diethylammonium-p-tert-butylcalix[6]arene dianion is reported. The calix moiety adopts a 1,2,3 alternate conformation, with one ammonium as exo-calix and other as endo-calix, with an intricate array of hydrogen bonds between phenol, phenolate and ammonium cations.     

Structure of premixed flames of propylene oxide: Molecular beam mass spectrometric study and numerical simulation

The knowledge of the combustion chemistry of oxygenated fuels is essential for the development of detailed kinetic mechanisms suitable for the combustion processes involving biofuels. Moreover, epoxidized olefins, are increasingly used as chemical intermediates or as bulk chemicals. Nevertheless, a dearth of data for their reactivity in the oxidative environment can be observed in the current literature. This study reports the experimental and the model characterization of the flame structure of propylene oxide at stoichiometric and fuel-rich conditions at atmospheric pressure. To this aim, the species mole fractions in three premixed flames stabilized on a flat-flame burner have been quantitatively measured by using the flame sampling molecular beam mass spectrometry. Three chemical kinetic mechanisms retrieved from the current literature involving propylene oxide chemistry have been validated against the novel experimental data. In general, the predictions appeared to be in satisfactory agreement with measurements except for acetaldehyde and ketene. The rate of production analysis in the flame has shown that the discrepancies observed for these species are related basically to the incorrect ratio between the rates of primary reaction pathways of propylene oxide destruction.