Thermophysical Properties of CeB6 and PrB6 at subambient temperatures

Equilibrium adiabatic heat-capacity measurements have been made on zone refined samples of CeB₆ and PrB₆. Companion measurements made on LaB₆, NdB₆, and GdB₆ have been reported elsewhere. These show cooperative lambda-type anomalies associated with antiferro-magnetic ordering. Except for lanthanum hexaboride, Schottky internal crystal field levels result in significant contributions to the thermodynamic functions. The gross thermodynamic properties at 298.15 K heat capacity (C_p/R), entropy increment (Δ^T _0,m S ⁰/R), and Gibbs energy function are correlated with the nature of the lanthanide. For LaB₆, CeB₆, PrB₆, NdB₆, and GdB₆ the three properties are, respectively: {11.654, 12.014, 11.997, 11.916, 11.695} Cp/R; {10.001, 11.803, 12.430, 12.558, 13.982} S⁰/R, and finally {4.379, 5.912, 6.232, 6.451, 7.905}Φ⁰ _m/R. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mixed system of Eudragit s-100 with a designed amphipathic peptide: control of interfacial elasticity by solution composition

We report an interfacially active system based on an informational peptide surfactant mixed with an oppositely charged polyelectrolyte. The 21-residue cationic peptide, AM1, has previously been shown to respond reversibly to pH and metal ions at fluid interfaces, forming elastic films that can be rapidly switched to collapse foams or emulsions on demand. Here we report the reversible association of AM1 with the methacrylate-based anionic polymer Eudragit S-100. The strength of the association, in bulk aqueous solution, is modulated by added metal ions and by ionic strength. Addition of zinc ions to the peptide-polymer system promotes complex formation and phase separation, while addition of a chelating agent reverses the association. The addition of salt weakens peptide-polymer interactions in the presence or absence of zinc. At the air-water interface, Eudragit S-100 forms an elastic mixed film with AM1 in the absence of metal, under conditions where the peptide alone does not show interfacial elasticity. When zinc is present, the elasticity of the mixed film is increased, but the rate of interfacial adsorption slows due to formation of peptide-polymer complexes in bulk solution. An understanding of these interactions can be used to identify favorable foam-forming conditions in the mixed system.     

Antibacterial effects of carbon nanotubes: size does matter!

We provide the first evidence that the size (diameter) of carbon nanotubes (CNTs) is a key factor governing their antibacterial effects and that the likely main CNT-cytotoxicity mechanism is cell membrane damage by direct contact with CNTs. Experiments with well-characterized single-walled carbon nanotubes (SWNTs) and multiwalled carbon nanotubes (MWNTs) demonstrate that SWNTs are much more toxic to bacteria than MWNTs. Gene expression data show that in the presence of both MWNTs and SWNTs, Escherichia coli expresses high levels of stress-related gene products, with the quantity and magnitude of expression being much higher in the presence of SWNTs.     

Infrared spectroscopy of isolated nucleotides. 1. The cyclic 3′,5′-adenosine monophosphate anion

The intracellular second messenger deprotonated adenosine 3′,5′-cyclic monophosphate anion (cAMP-H)⁻, generated as gaseous species by electrospray ionization (ESI) and stored in a Paul ion-trap mass spectrometer, has been investigated by mass-resolved infrared multiple photon dissociation (IRMPD) spectroscopy in the 900–1800 cm⁻¹ fingerprint wavenumber range, exploiting the powerful and continuously tunable radiation from a free electron laser (FEL) at the Centre Laser Infrarouge d’Orsay (CLIO). The IRMPD features are interpreted by comparison with the IR spectra obtained by quantum chemical calculations for different low-lying conformers, allowing an assignment for the observed IRMPD bands. It is to be noted that the calculated IR spectra for the most stable conformers look all rather similar and do not allow an unambiguous structural assignment, based exclusively on the IRMPD spectrum. However, the positions and intensities of the IRMPD features of isolated (cAMP-H)⁻ ions are consistent with a species deprotonated at the phosphate group and compatible with the main equilibrium structures lying within 18 kJ mol⁻¹ from the lowest lying conformation, the anti-chair form with a C3′-endo sugar twist.     

DNA closed nanostructures: a structural and Monte Carlo simulation study

DNA nanoconstructs are obtained in solution by using six unique 42-mer DNA oligonucleotides, whose sequences have been designed to form a pseudohexagonal structure. The required flexibility is provided by the insertion of two non-base-paired thymines in the middle of each sequence that work as flexible hinges and constitute the corners of the nanostructure when formed. We show that hexagonally shaped nanostructures of about 7 nm diameter and their corresponding linear open constructs are formed by self-assembly of the specifically designed linear oligonucleotides. The structural and dynamical characterization of the nanostructure is obtained in situ for the first time by using dynamic light scattering (DLS), a noninvasive method that provides a fast dynamic and structural analysis and allows the characterization of the different synthetic DNA nanoconstructs in solution. A validation of the LS results is obtained through Monte Carlo (MC) simulations and atomic force microscopy (AFM). In particular, a mesoscale molecular model for DNA, developed by Knotts et al., is exploited to perform MC simulations and to obtain information about the conformations as well as the conformational flexibilities of these nanostructures, while AFM provides a very detailed particle analysis that yields an estimation of the particle size and size distribution. The structural features obtained by MC and AFM are in good agreement with DLS, showing that DLS is a fast and reliable tool for characterization of DNA nanostructures in solution.     

Optimisation of aqueous synthesis of iron oxide nanoparticles for biomedical applications

Iron oxide nanoparticles (IONPs) were prepared via aqueous synthesis which combines alkaline co-precipitation (CP) of ferric and ferrous precursors with mild hydrothermal (HT) treatment without cupping agents (CA). In this novel synthesis route, CP + HT, we found the optimal synthesis conditions to obtain IONPs without a second phase and with the size larger than in standard CP: the equal number of Fe(II) and Fe(III) ions are co-precipitated with 6 M ammonia and further HT treated in mild conditions (120 °C for 24 h) without CA. The IONPs obtained by novel CP + HT route had faceted rectangular morphology, a mean TEM diameter of 21.5 ± 6.3 nm, a hydrodynamic diameter of 30.2 ± 9.1 nm and a zeta potential at pH 4 of 48.2 ± 0.6 mV. After the subsequent oxidation step, the final product (IONPs) was studied by XRD, FTIR and XPS, which confirmed the desired structure of γ-Fe₂O₃. Importantly, this synthesis was especially planned for the preparation of IONPs for biomedical applications. Thus, our novel synthesis was designed to be compliant with the regulations of nano-safety: no special atmosphere, no complex multistep size separation, no organic solvents or solvent exchange, no CA and their washing and the use of low temperature in the final optimised conditions. In addition, this simple synthesis route combines the CP and HT methods, which are both proven to be scalable. Moreover, repeatability and reproducibility of the optimal CP + HT synthesis were confirmed on the lab-scale; more than 100 repetitions with different dishes, different operators and different batches of chemicals were performed.     

Oil-in-water nanocontainers as low environmental impact cleaning tools for works of art: two case studies

A novel class of p-xylene-in-water microemulsions mainly based on nonionic surfactants and their application as low impact cleaning tool in cultural heritage conservation is presented. Alkyl polyglycosides (APG) and Triton X-100 surfactants allow obtaining very effective low impact oil-in-water (o/w) microemulsions as alternatives to pure organic solvents for the removal of polymers (particularly Paraloid B72 and Primal AC33) applied during previous conservation treatments. The ternary APG/p-xylene/water microemulsions have been characterized by quasi elastic light scattering to obtain the hydrodynamic radius and the polydispersity of the microemulsion droplets. Laplace inversion of the correlation function CONTIN analysis provided evidence of acrylic copolymers solubilization into the oil nanodroplets. Contact angle, Fourier transform infrared (FTIR), and scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS) data confirmed that microemulsions were effective in removing polymer coatings. The phase diagram of APG microemulsions showed that a reduction >90% (compared to the conventional cleaning methods) of the organic solvent can be achieved by using o/w microemulsions. The microemulsions were successfully tested in two real cases: (1) the APG based microemulsion was used in a Renaissance painting by Vecchietta in Santa Maria della Scala, Siena, Italy, degraded by the presence of a polyacrylate coating applied during a previous restoration and (2) a Triton X-100 oil-in-water microemulsion containing (NH4)2CO3 in the water continuous phase. The association of ammoniun carbonate to the microemusion led to the swelling of an organic deposit (mainly asphaltenes deposited on the fresco in the Oratorio di San Nicola al Ceppo in Florence, still contamined by the water of the Arno river during the 1966 flood) and a very efficient removal of highly insoluble inorganic deposits (mainly gypsum) strongly associated to asphaltenes. These innovative systems are very attractive for the low amount of organic solvent used to extract the polymers or highly insoluble substances as the asphaltene and the very efficient and mild impact of the cleaning procedure on the fragile painted surfaces.     

Stereochemical features making deoxycholic acid derived tropos biphenylphosphites efficient chiral ligands for rhodium: the asymmetric hydrogenation of dimethylitaconate as a case study

Different deoxycholic acid derived biphenylphosphites, whose tropos nature was ascertained by NMR and CD measurements, were used in the rhodium-catalyzed asymmetric hydrogenation of dimethylitaconate achieving enantiomeric excesses up to 91%. The comparison of these results to those obtained using the corresponding atropoisomeric binaphthyl analogues, together with NMR and CD measurements on the rhodium complexes of some phosphites, allowed us to shed light on the nature of the active catalytic species and on the asymmetric induction process and hence to recognize the most appropriate stereochemical features to reach good levels of enantioselectivity.