Ancient Roman wall paintings mapped nondestructively by portable NMR

The stratigraphies of decorated walls in ancient Herculaneum, Italy, were analyzed by single-sided ¹H NMR. A large version of the NMR-MOUSE® with a maximum penetration depth of 25 mm was used to map proton density profiles at different positions of the Mosaic of Neptune and Amphitrite showing considerable differences between different tesserae and the mortar bed at different times of the year. In the House of the Black Room, different mortar layers were observed on painted walls as well as different proton content in different areas due to different moisture levels and different conservation treatments. The proton density profiles of the differently treated areas indicated that one method leads to higher moisture content than the other. Untreated wall paintings from different times were profiled in a recently excavated room at the Villa of the Papyri showing two different types of mortar layer structures which identify two different techniques of preparing the walls for painting. Reflectance Fourier mid-infrared spectroscopy and in situ X-ray fluorescence measurements complemented the NMR measurements and provided additional insight into the identification of organic coatings as well as the nature of the pigments used, respectively. The information acquired nondestructively by NMR is valued for elaborating conservation strategies and for identifying different schools of craftsmen who prepared the mortar supports of the wall paintings.     

Thermal study on complexes with Schiff base derived from 1,2,4-triazole as potential antimicrobial agents

In order to develop new metallo-antimicrobials the complexes of type MLCl·nH₂O ((1) M: Co, n = 0; (2) M: Ni, n = 2; (3) M: Cu, n = 2.5; (4) M: Zn, n = 0, HL: Schiff base derived from acetylacetone and 3-amino-4H-1,2,4-triazole) were synthesized by template condensation. The features of complexes have been assigned from microanalytical, IR and UV–Vis-NIR data. The species heating in air evidenced processes as melting, water and hydrochloride endothermic elimination as well as oxidative degradation of the Schiff base. The temperature ranges as well as modification in the electronic spectra of dehydrated intermediates indicate the presence of both coordination and crystallisation water molecules. The final product of decomposition was the most stable metal oxide as powder X-ray diffraction indicated.     

Analysis of peptides and proteins using sub-2 μm fully porous and sub 3-μm shell particles

The objective of this study was to evaluate the potential of sub-2 μm totally porous particles and sub-3 μm shell particles for peptide and protein analysis. Specific analytical strategies must be developed for these biomolecules as their importance in the pharmaceutical industry increases and as their structural complexity involves some issues when classical LC conditions are employed. Attention was paid on comparing these different columns in various LC conditions (different temperatures, gradient times, and mobile phase flow rates). The comparison of the different supports was assessed considering columns characteristics (quality of packing, silanol activity, pore size, totally porous or shell particles). In this article, peptides were first analyzed with both column technologies. Similar results to those achieved with low molecular weight compounds were obtained (peak capacity >100 for t_grad around 3 min and columns dimensions of 2.1 mm id × 50 mm), but specific conditions were required (elevated temperature and the use of a volatile ion-pairing reagent, namely TFA). For peptide analysis following tryptic digestion, the goal was to improve peak capacity and resolution because of the large number of generated peptides. For this purpose, longer columns packed with porous sub-2 μm or shell sub-3 μm particles (i.e., 150 mm) and gradient times (i.e., up to 30 min) were tested. On the other hand, proteins in their intact forms have higher molecular weights (MW > 5000 Da) and a tertiary structure, thus requiring different conditions in terms of stationary phase hydrophobicity (C₄vs. C₁₈) and pore size (300 vs. 120 Å). In addition, there were issues with adsorption onto the LC system and/or the column itself. This study showed that proteins with MWs lower than 40,000 Da required chromatographic conditions close to those employed for peptide analysis. For larger proteins, a C₄ 300 Å stationary phase gave the best results, confirming theoretical predictions.     

A quantitative, real-time assessment of binding of peptides and proteins to gold surfaces

Interactions of peptides and proteins with inorganic surfaces are important to both natural and artificial systems; however, a detailed understanding of such interactions is lacking. In this study, we applied new approaches to quantitatively measure the binding of amino acids and proteins to gold surfaces. Real‐time surface plasmon resonance (SPR) measurements showed that TEM1‐β‐lactamase inhibitor protein (BLIP) interacts only weakly with Au nanoparticles (NPs). However, fusion of three histidine residues to BLIP (3H‐BLIP) resulted in a significant increase in the binding to the Au NPs, which further increased when the histidine tail was extended to six histidines (6H‐BLIP). Further increasing the number of His residues had no effect on the binding. A parallel study using continuous (111)‐textured Au surfaces and single‐crystalline, (111)‐oriented, Au islands by ellipsometry, FTIR, and localized surface plasmon resonance (LSPR) spectroscopy further confirmed the results, validating the broad applicability of Au NPs as model surfaces. Evaluating the binding of all other natural amino acid homotripeptides fused to BLIP (except Cys and Pro) showed that aromatic and positively‐charged residues bind preferentially to Au with respect to small aliphatic and negatively charged residues, and that the rate of association is related to the potency of binding. The binding of all fusions was irreversible. These findings were substantiated by SPR measurements of synthesized, free, soluble tripeptides using Au‐NP‐modified SPR chips. Here, however, the binding was reversible allowing for determination of binding affinities that correlate with the binding potencies of the related BLIP fusions. Competition assays performed between 3H‐BLIP and the histidine tripeptide (3 His) suggest that Au binding residues promote the adsorption of proteins on the surface, and by this facilitate the irreversible interaction of the polypeptide chain with Au. The binding of amino acids to Au was simulated by using a continuum solvent model, showing agreement with the experimental values. These results, together with the observed binding potencies and kinetics of the BLIP fusions and free peptides, suggest a binding mechanism that is markedly different from biological protein–protein interactions.     

Facile synthesis of phosphorylated azides in ionic liquids and their use in the preparation of 1,2,3‐triazoles

The facile general synthetic route to azidoalkylphosphonates by the nucleophilic substitution reaction in a series of bromoalkylphosphonates was elaborated, using 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]) as a recyclable reaction medium. These azidoalkylphosphonates were used as intermediates for copper(I)‐catalyzed regioselective 1,3‐dipolar cycloaddition with a variety of alkynes to afford 4‐substituted (1H‐1,2,3‐triazol‐1‐yl)alkylphosphonates as potential drug candidates. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:293–300, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20420     

Magnetization Switching in the GdFeCo Films with In-Plane Anisotropy via Femtosecond Laser Pulses

Ferrimagnetic rare-earth substituted metal alloys GdFeCo were shown to exhibit the phenomenon of all-optical magnetization switching via femtosecond laser pulses. All-optical magnetization switching has been comprehensively investigated in out-of-plane magnetized GdFeCo films; however, the films with the in-plane magnetic anisotropy have not yet been studied in detail. We report experimental observations of the magnetization switching of in-plane magnetized GdFeCo films by means of the femtosecond laser pulses in the presence of a small magnetic field of about 40 µT. The switching effect has a threshold both in the applied magnetic field and in the light intensity.     

Butyllithium Addition to α‐Chiral Compounds: Solvent Mixture Effects on Diastereofacial Selectivity

Temperature‐dependent selectivity in nucleophilic additions is affected by the solvent. In this context, we investigated the effect on diastereoselectivity of solvent mixtures with respect to pure solvents. Binary systems of THF/hexane and of four different hydrocarbon mixtures were employed in BuLi addition to 2‐phenylpropanal, (2S)‐2‐[(tert‐butyl)dimethylsilyloxy]‐2‐phenylethanal, and (2S)‐2‐[(tert‐butyl)dimethylsilyloxy]‐N‐(trimethylsilyl)propan‐1‐imine. A 5‐mol‐% of THF in hexane affects the isomer ratio by reducing both ΔΔH^≠ and ΔΔS^≠ contributions, and suppresses T_inv. On the contrary, in hydrocarbon binary mixtures, the T_inv is still observed and occurs at a higher temperature than in pure solvents. Studying the dependence of T_inv on the hexane/decane mixture composition, we propose the formation of a peculiar solvation cluster that is unaffected by the composition of the bulk reaction solvent.     

Recent advances in laser self-injection locking to high-Q microresonators

The stabilization and manipulation of laser frequency by means of an external cavity are nearly ubiquitously used in fundamental research and laser applications. While most of the laser light transmits through the cavity, in the presence of some back-scattered light from the cavity to the laser, the self-injection locking effect can take place, which locks the laser emission frequency to the cavity mode of similar frequency. The self-injection locking leads to dramatic reduction of laser linewidth and noise. Using this approach, a common semiconductor laser locked to an ultrahigh-Q microresonator can obtain sub-Hertz linewidth, on par with state-of-the-art fiber lasers. Therefore it paves the way to manufacture high-performance semiconductor lasers with reduced footprint and cost. Moreover, with high laser power, the optical nonlinearity of the microresonator drastically changes the laser dynamics, offering routes for simultaneous pulse and frequency comb generation in the same microresonator. Particularly, integrated photonics technology, enabling components fabricated via semiconductor CMOS process, has brought increasing and extending interest to laser manufacturing using this method. In this article, we present a comprehensive tutorial on analytical and numerical methods of laser self-injection locking, as well a review of most recent theoretical and experimental achievements.