An Improved Measurement of Isotopic Ratios by High Resolution Mass Spectrometry

The study of protein kinetics requires an accurate measurement of isotopic ratios of peptides. Although Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometers yield accurate mass measurements of analytes, the isotopologue ratios are consistently lower than predicted. Recently, we demonstrated that the magnitude of the spectral error in the FT-ICR mass spectrometer is proportional to the scan duration of ions. Here, we present a novel isotopic ratio extrapolation (IRE) method for obtaining accurate isotopic ratio measurements. Accuracy is achieved by performing scans with different duration and extrapolation of the data to the initial moment of the ion rotation; IRE minimizes the absolute isotopic ratio error to ≤1 %. We demonstrate the application of IRE in protein turnover studies using ²H₂O-metabolic labeling. Overall, this technique allows accurate measurements of the isotopic ratios of proteolytic peptides, a critical step for enabling routine studies of proteome dynamics.      

Calorimetric, conductometric and density measurements of iteratively filtered water using 450, 200, 100 and 25 nm Millipore filters

This study presents some experimental results on the variation of the physico-chemical properties of pure MilliQ water, when subjected to a procedure of iterated filtration through Millipore filters with porosity ranging from 450 to 25 nm. The parameters measured were: calorimetry, electrical conductivity, density, and pH. Release of chemical impurities can be ruled out due to the nature of the materials used. As in the case of iteratively filtered water prepared using Pyrex glass filters, the specific electrical conductivity and the pH were found to increase with increasing number of iterations. There was also a dependence on the average pore size of the filters. The idea of water as a system capable of self-organization triggered by various perturbations (mechanical and/or electromagnetic) is gaining momentum. It responds to such perturbations by forming dissipative structures, i.e., far-from-equilibrium systems.     

Polarity and steric effect of the lateral substituent on the mesophase behaviour of some newly prepared liquid crystals

Eight homologous series of 2- (or 3-) substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_a–h) were prepared in which, within each homologous series, the length of the terminal alkoxy group varies between 6, 8, 10 and 12 carbons, while the other substituent, X, is a laterally attached polar group that alternatively changed from CH₃, H, F, Br and CN. Compounds prepared were characterised by infrared and ¹H-NMR spectroscopy, and their mesophase behaviour investigated by differential scanning calorimetry and identified by polarised light microscopy. The results were discussed in terms of polarity and steric effects. The stability of the mesophase was correlated once with the dipolar anisotropy of the whole molecule and another with the dipolar anisotropy of the substituent, X. A comparative study was made between the investigated compounds and their previously prepared linear 4-substituted isomers, namely 4-substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_i–k).     

Environmental certification: a scientific tool for sustainability. Evaluation of possible indicators for the environmental performance evaluation (EPE) of Ravenna province (Italy)

Environmental certification is becoming the main tool for application of sustainable development principles. The European Regulation Emas and the international standard ISO 14001 both require for certification, to perform an environmental management system to prevent environmental impacts and to continuously improve environmental performance. For a good environmental performance evaluation (EPE), certification needs to use scientific methodologies and to interface with scientific research; here we proposed emergy analysis as a valid method for EPE and emergetic environmental performance and condition indicators (EPIs, ECIs) to monitor a territorial system: Ravenna province (Italy). Together with emergy indicators were selected other indicators for a deeper EPE: emitted/adsorbed CO2, energy consumptions, air and water pollution measures. The paper showed that Ravenna system has a good environmental performance and demonstrated how different indicators from the most advanced chemical research (chemical-physical, analytical, etc.) contribute to a complete EPE of a complex territorial system and are useful for environmental certification and sustainable development.     

Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

The structurally precise Cu‐rich hydride nanoclusters [PdCu₁₄H₂(dtc/dtp)₆(C≡CPh)₆] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu₂₈H₁₅(S₂CNⁿBu₂)₁₂]⁺ or [Cu₂₀H₁₁{S₂P(OⁱPr)₂}₉] with phenyl acetylene in the presence of Pd(PPh₃)₂Cl₂. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd⁰ and four Cu^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH₂]^2? unit and its Cu₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.     

Electrochemical Sensor Based on Thioether Oligomer Poly(N‐vinylpyrrolidone)‐modified Gold Electrode for Bisphenol A Detection

Presently, bisphenol A (BPA) has been added to the list of substances of very high concern as endocrine disruptors. According to the literature, exposure to bisphenol A even at low doses may result in adverse health effects. In this study, electrochemical sensor of Bisphenol A based on thioether DDT‐Poly(N‐vinylpyrrolidone) oligomer has been developed. The thioether oligomer, which is capable of recognizing BPA, was prepared and used for gold electrode modification. The characterization of the modified gold electrode and the synthesized thioether oligomer were carried out by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM), Fourier‐transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (¹H NMR) and Size exclusion chromatography (SEC). Obtained results indicate that the modified electrode shows good electrochemical activity, good sensitivity and reproducibility for BPA detection. It exhibited a good linear relationship ranging from 1 to 20 pg/mL, and the detection limit was found to be 1.9 pg/mL at S/N=3. Several interfering species such as hydroquinone, phenol and resorcinol were used and their behaviors on the modified gold electrode were investigated.     

Snail Hepatopancreatic Lipase: A New Member of Invertebrates Lipases' Group

Higher animal's lipases are well characterized; however, much less is known about lipases from mollusks. A lipolytic activity was located in the land snail (Eobania vermiculata) digestive glands (hepatopancreas), from which a snail digestive lipase (SnDL) was purified. Pure SnDL has a molecular mass of 60 kDa; it does not present the interfacial activation phenomenon. It was found to be more active on short-chain triacylglycerols than on long-chain triacylglycerols. The NH₂-terminal sequence of the SnDL shows 66% of identity with the 17 NH₂-terminal amino acids of a putative lipase from sea urchin (Strongylocentrotus purpuratus). No sequence identity was found with known lipases. Interestingly, neither colipase nor bile salts were detected in the snail hepatopancreas. This suggests that colipase evolved in vertebrates simultaneously with the appearance of an exocrine pancreas and a true liver which produces bile salts. Altogether, these results suggest that SnDL is a member of a new group of digestive lipases belonging to invertebrates.     

Simple and efficient cleavage reaction of the boc group in heterocyclic compounds

Dedicated to the memory of Pr. Ladjama Daif A series of chiral cyclosulfamides have been synthesized by alkaline cyclisation starting from N‐benzoylamino acids (Ala, Val, Leu, Phe) derivatives and chlorosulfonyl isocyanate. A simplified and regioselective deprotection of the cyclic compounds (cyclosulfamides) containing the tert‐butyloxycarbonyl group (Boc) has been achieved in good yield by fusion under reduced pressure.     

Cyclic PNA-based compound directed against HIV-1 TAR RNA: modelling, liquid-phase synthesis and TAR binding

A cyclic molecule including a hexameric PNA sequence has been designed and synthesized in order to target the TAR RNA loop of HIV-1 through the formation of a "kissing complex". For comparison, its linear analogue has also been investigated. The synthesis of the cyclic and linear PNA has been accomplished following a liquid-phase strategy using mixed PNA and fully N-protected (aminoethylglycinamide) fragments. The interactions of this cyclic PNA and its linear analogue with TAR RNA have been studied and the results indicate clearly that no interaction occurs between the cyclic antisense PNA and TAR RNA, whereas a tenuous interaction has been detected with its linear PNA analogue.