MIP sensors – the electrochemical approach

This review highlights the importance of coupling molecular imprinting technology with methodology based on electrochemical techniques for the development of advanced sensing devices. In recent years, growing interest in molecularly imprinted polymers (MIPs) in the preparation of recognition elements has led researchers to design novel formats for improvement of MIP sensors. Among possible approaches proposed in the literature on this topic, we will focus on the electrosynthesis of MIPs and on less common hybrid technology (e.g. based on electrochemistry and classical MIPs, or nanotechnology). Starting from the early work reported in this field, an overview of the most innovative and successful examples will be reviewed.     

Phonon dynamics and electron-phonon coupling in pristine picene

The paper reports a complete analysis of the phonon structure of crystalline picene, a recently announced organic semiconductor. Both lattice and intramolecular vibrations are investigated. An exhaustive assignment of lattice phonons is obtained through polarized Raman spectra assisted by lattice dynamics calculations based on a well tested atom-atom potential model. Raman, infrared spectra and density functional (DFT) calculations are used for the characterization of intramolecular modes. Coupling between low-frequency molecular vibrations and lattice phonons is accounted for. Molecule-to-molecule transfer integrals, as well as the Peierls and Holstein (non-local and local) coupling constants, are evaluated through the semiempirical method INDO/S (Intermediate Neglect of Differential Overlap with Spectroscopic parametrization).     

Transient photothermal spectra of plasmonic nanobubbles

The photothermal efficacy of near-infrared gold nanoparticles (NP), nanoshells, and nanorods was studied under pulsed high-energy optical excitation in plasmonic nanobubble (PNB) mode as a function of the wavelength and duration of the excitation laser pulse. PNBs, transient vapor nanobubbles, were generated around individual and clustered overheated NPs in water and living cells. Transient PNBs showed two photothermal features not previously observed for NPs: the narrowing of the spectral peaks to 1 nm and the strong dependence of the photothermal efficacy upon the duration of the laser pulse. Narrow red-shifted (relative to those of NPs) near-infrared spectral peaks were observed for 70 ps excitation laser pulses, while longer sub- and nanosecond pulses completely suppressed near-infrared peaks and blue shifted the PNB generation to the visual range. Thus, PNBs can provide superior spectral selectivity over gold NPs under specific optical excitation conditions.     

HPLC-ESI-MS and MS/MS structural characterization of multifucosylated N-glycoforms of the basic proline-rich protein IB-8a CON1+ in human saliva

This study describes the characterization of the glycan moieties and the peptide backbone of six glycoforms of IB-8a CON1(+), a basic proline-rich protein present in human saliva. MS analyses on the intact glycoproteins before and after N-deglycosylation with PNGase F and high-resolution MS/MS sequencing by LTQ Orbitrap XL of peptides and glycopeptides from tryptic digests allowed the structural characterization of the glycan moieties and the polypeptide backbone, as well as to establish the glycosylation site at the asparagine residue at 98th position. Five of the glycoforms carry a biantennary N-linked glycan fucosylated in the innermost N-acetylglucosamine of the core and showing from zero to four additional fucoses in the antennal region. The sixth glycoform carries a monoantennary monofucosylated oligosaccharide. The glycoform cluster was detected on 28 of 71 adult saliva specimens. Level of fucosylation showed interindividual variability with the major relative abundance for the trifucosylated glycoform. Nonglycosylated IB-8a CON1(+) and the variant IB-8a CON1(-), lacking of the glycosylation site, have been also detected in human saliva.     

Liquid chromatography/tandem mass spectrometry for the identification and determination of trichothecenes in maize

A reliable, sensitive and selective liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed to determine four trichothecene mycotoxins (nivalenol, deoxynivalenol, fusarenon X and 3-acetyldeoxynivalenol) in maize. Sample preparation was performed by extracting the analytes with a mixture of acetonitrile and water, followed by a solid-phase extraction with Carbograph-4 cartridges as the purification step. For the LC/MS/MS analysis two interfacing systems, Turbo IonSpray (TISP) and atmospheric pressure chemical ionization (APCI), were compared in both negative and positive ion modes. LC and MS parameters were optimized to achieve better results and sensitivity. The effect of mobile phase modifiers such as ammonium acetate and formic acid on the ionization yield was also evaluated. The best results were obtained using the electrospray ionization (ESI) interface in negative ion mode and the multiple reaction monitoring mode (MRM) for the quantitation. The detection limits ranged between 10 ng/g for fusarenon X and 1.5 ng/g for deoxynivalenol. A linear working range was achieved with a standard deviation between 3 and 10% and recovery rates from the maize samples above 81%. The procedure was applied to the analysis of a set of maize samples collected from farms located in different areas of northern and central Italy. The investigated samples turned out to be contaminated primarily with deoxynivalenol and, to a minor extent, with its derivatives.     

The Michael addition of indoles to alpha,beta-unsaturated ketones catalyzed by CeCl3.7H2O-NaI combination supported on silica gel

Alkylation of indoles by means of the Michael addition has been the subject of a number of investigation. It is well established that regioselectivity in the additions of indoles to electron-deficient alkenes is strongly controlled by the reaction medium. In a continuation of the work on developing greener and cleaner technologies, the cerium(III) chloride heptahydrate and sodium iodide combination supported on silica gel catalyzes the alkylation of various indoles with alpha,beta-unsaturated ketones giving 3-(3-oxoalkyl)indole derivatives in good yields. The substitution on the indole nucleus occurred exclusively at the 3-position, and N-alkylation products have not been observed.     

Oriented thin films from soluble polythiophenes

The degree of orientation of thin films of eight different polymeric structures, belonging to the class of soluble polyalkylthiophenes (PATs) has been studied. Thin films of the polymers, obtained by spin coating onto glass substrates, were oriented by means of the rubbing technique. The degree of orientation is related to the regioregularity of the system: highly regioregular polymers can be oriented, while regiorandom materials are not oriented. The degree of orientation can be improved by thermal annealing of the oriented films. As a result of annealing, which was performed at different temperatures according to the thermal behavior of the polymers, it was possible to increase the polarization ratio for poly(3-decylthiophene) up to 12–13 as detected from the UV-vis spectra in polarized light. Moreover in the investigated PATs, both the key role of molecular weight and its distribution for achieving a high orientation degree has been assessed. Copyright © 2003 John Wiley & Sons, Ltd.     

Hybrid organo-inorganic clay with nonionic interlayers. mid- and near-IR spectroscopic studies

The intercalation of organic polymers molecules (i.e., PEGs and BRIJ) into a standard Ca-montmorillonite has been studied by XRD, TG, and IR spectroscopy. The polymer intercalation is confirmed by the increasing of the d(001) in XRD spectra as well as by the complex multisteps thermal decomposition behavior of the organo-clay materials. Mid-IR and diffuse reflectance near-IR spectra of the intercalated materials show the polymer diagnostic bands (CH stretching and deformation mode), shifted or changed in shape by the interaction with the clay matrix. Both PEG 1500 and PEG 4000 based materials are likely intercalated in an extended configuration, similar to the amorphous polymer form. BRIJ intercalated polymer spectra suggest the disordered conformation of the alkilic chain in a prevailing "gauche", poorly packed, conformation. Host montmorillonite IR bands, mainly OH and water stretching and deformation fundamentals, combination, and overtone bands, are reduced in intensity by polymer intercalation, pointing out an interaction, likely through H-bonding and/or a possible substitution of cations hydration water molecules.     

Two step, hydrolytic-solvothermal synthesis of redispersible titania nanocrystals and their gas-sensing properties

A titanium chloromethoxide solution was prepared by reacting TiCl₄ with methanol, followed by water addition. The starting solutions were characterized by Fourier Transform Infrared (FTIR) spectroscopy, evidencing that the in situ generated water results in early hydrolysis of the chloroalkoxide. The solution was reacted with molten dodecylamine at room temperature, obtaining a white slurry of amorphous titania nanoparticles. Stable, redispersible TiO₂ nanocrystals could be prepared by subsequent solvothermal treatment in oleic acid at 250???C. The use of oleic acid was essential for obtaining crystalline structures, while other surfactants prevented crystallization. The nanocrystals were characterized by X-ray Diffraction and Transmission Electron Microscopy, confirming the formation of anatase TiO₂ nanocrystals with a mean size of 3.3?nm. The TiO₂ nanocrystals were used for fabricating gas-sensing devices, which were tested towards ethanol vapors. The initial small size of the nanocrystals, and the limited size growth during the high-temperature sensor operation, result in remarkable sensing performances if compared with bulk titania sensors.