Small strain and moderate rotation

Kinematical assumptions leading to the approximate theory of small strain accompanied by moderate rotations are discussed with reference to a three-dimensional continuous body. In particular, the relationship with Korn's inequality is examined. It is found that for bounded bodies the coincidence of small strain and moderate rotation on subsets of non-zero volume measure is not possible. Two explicit examples are presented to illustrate this point.     

New trends in the analysis of masonry structures

The modern theory of masonry structures has been set up on the hypothesis of no-tension behaviour, with the aim of offering a reference model, independent of materials and building techniques employed. This hypothesis gives rise to inequalities which have to be satisfied by the stress tensor components and, as a dual aspect, to the kinematic behaviour characteristics of media which can be classified as lying between solids and fluids: the structure of the masonry material consists of particles reacting elastically only when in contact. An examination of the plane-stress problem leads us to define, within the prescribed domain under admissible loads, three different subdomains with null, regular, or non-regular principal stress tensors, respectively. As the boundaries of such subdomains are not known a priori, the problem can be classified as a free boundary value problem. The analysis concerns mainly the subdomains where the stress tensor is non-regular; and a non-regularity condition det =0 is added to the equilibrium equations. This condition makes the stress problem isostatic and leads to a violation of Saint-Venant's compliance conditions on strains. Hence there is a need to introduce a strain tensor, not related to the stress tensor, which can be decomposed into an extensional component and a shearing component; we prove that such strains, of the class ^c, are similar to those of the theory of plastic flow. From the point of view of computational analysis the anelastic strains are considered as given distortions; they are computed by means of the Haar-Kármán principle, modified for computational purposes by an idea of Prager and Hodge.

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Sommario La moderna teoria delle strutture murarie, fondata sulla rigorosa non reagenza a trazione del materiale, ha lo scopo di fornire un modello di riferimento indipendente sia dalle caratteristiche del materiale sia dalle techniche costruttive impiegate. L'ipotesi di non reagenza a trazione si traduce in disuguaglianze che le componenti del tensore di stress devono verificare; dualmente il comportamento caratteristico cinematico può esser classificato di confine, come del resto la stessa statica, tra solidi e fluidi: la struttura ipotizzata del materiale muratura consiste di particelle che reagiscono solo se sono in contatto. L'esame del problema piano porta a definire all'interno del dominio di definizione tre differenti tipi di sub-regioni in cui lo stress è nullo, canonico, o singolare. Poiché le frontiere di queste sub-regioni non sono note a priori il problema può anche essere classificato di frontiera libera. L'analisi concerne fondamentalmente la sub-regione in cui il tensore è non regolare, perché deve verificare anche la condizione det =0. Ciò rende isostatico il problema e conduce anche alla violazione della condizione di integrabilità delle deformazioni. Questo passaggio può essere superato introducendo un tensore di deformazioni a tensioni nulle che si può decomporre in una componente estensionale ed in una componente di scorrimento; si dimostra che queste deformazioni sono equivalenti a quelle che intervengono nella Teoria del flusso plastico. Dal punto di vista computazionale le deformazioni anelastiche sono considerate come distorsioni impresse determinate attraverso il principio di Haar-Kármán modificato, per le techniche computazionali, su idee di Prager e Hodge.

     

Natural estrogens in dairy products: Determination of free and conjugated forms by ultra high performance liquid chromatography with tandem mass spectrometry

Natural estrogens are synthesized by mammals in different amounts depending on the developmental stage and pregnancy/lactation period, and they may pass into milk, where they are mostly present as glucuronated and sulfated forms. In modern dairy practices, about 75% of milk is produced from pregnant cows; therefore, the amount of hormones that may pass into milk could be of concern. While estrogen determination in milk has been investigated in depth, the individual determination of estrogens and their conjugated forms in dairy products has not been fully addressed. The aim of this work was to develop and assess a sensitive method, using the peculiar retention properties of graphitized carbon black, to extract natural free estrogens and their major conjugated metabolites, without any enzymatic cleavage, from yogurt, cheese, and butter. The free and conjugated estrogens were eluted in two distinct fractions from the solid‐phase extraction cartridge and analyzed separately by ultra high performance liquid chromatography coupled to tandem mass spectrometry. Recoveries were higher than 80% for all the three sample typologies. The highest matrix effects were observed for butter, which was richest in lipid content, but was below 30%. A survey on some commercial dairy products suggests that production processes decreased estrogen content.     

Direct determination of total mercury in phosphate rock using alkaline fusion digestion

The aim of this work was to develop a new method to determine the mercury (Hg) concentrations in phosphate rock using a dedicated analytical instrument (the DMA80 Tricell by Milestone) that employs an integrated sequence of thermal decomposition followed by catalyst conversion, amalgamation and atomic absorption spectrophotometry. However, this instrument underestimates Hg concentrations when phosphorite and apatite rocks are investigated with a classic thermal decomposition treatment that complies with US EPA method 7473.     

An alternative quinoline synthesis by via Friedländer reaction catalyzed by Yb(OTf)3

Quinolines have been synthesized in very good yields from 2-aminoarylketones and differently substituted carbonyl compounds in the presence of Yb(OTf)₃ as the catalyst. The method is applicable to both cyclic and acyclic carbonyl compounds with only slight differences in the experimental procedure.     

Field-amplified online sample stacking capillary electrophoresis UV detection for plasma malondialdehyde measurement

Malondialdehyde (MDA) determination is the most widely used method for monitoring lipid peroxidation. Here, we describe an easy field-amplified sample injection (FASI) CE method with UV detection for the detection of free plasma MDA. MDA was detected within 8 min by using 200 mmol/L Tris phosphate pH 5.0 as running buffer. Plasma samples treated with ACN for protein elimination were directly injected on capillary without complex cleanup and/or sample derivatization procedures. Using electrokinetic injection, the detection limit in real sample was 3 nmol/L, thus improving of about 100-fold the LOD of the previous described methods based on CE. Precision tests indicate a good repeatability of our method both for migration times (CV = 1.11%) and for areas (CV = 2.05%). Moreover, a good reproducibility of intra- and inter-assay tests was obtained (CV = 2.55% and CV = 5.14%, respectively). Suitability of the method was tested by measuring MDA levels in 44 healthy volunteers.     

Fast and stable photochromic oxazines for fluorescence switching

The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level.     

Determination of the absolute configuration of the enantiomers of dihydroquinolines, isolated by chiral chromatography, by non empirical analysis of circular dichroism spectra and X-ray analysis

The enantiomers of racemic 3,4-dihydroquinolines with an acetal or thioacetal spiro ring and a quaternary stereogenic carbon have been isolated through semipreparative chiral chromatography using a polysaccharide-derived chiral stationary phase (Chiralpak AD) and n-hexane/ethanol as a mobile phase. The absolute configurations of the enantiomers of four compounds have been determined by a comparison of density functional theory (DFT) calculations of their electronic circular dichroism (ECD) spectra with the experimental ECD data. A detailed conformer population search to achieve a conformational average of these compounds was crucial, due to the flexibility of these molecules. The conformer distribution was evaluated by spartan 02 and the structure of each of the conformers found within 4 kcal/mol energy range was optimized with DFT. The final calculated ECD spectrum obtained after Boltzmann averaging was compared with the ECD spectrum of the less well retained enantiomer and the correlation (R)/(−) was established for all compounds. The monocrystals of both enantiomers of one compound were obtained from the HPLC eluates. Their absolute configurations were determined by X-ray crystallographic analysis and confirmed by ECD analysis. In all cases, the second-eluted enantiomer in chiral HPLC exhibits an (R)-configuration.     

Effect of substituents and protonation on the mechanism of 1,3-dipolar retro-cycloaddition reaction of pyrrolidino[60]- and [70]fullerenes

The mass spectra of new substituted pyrrolidino[60]- and [70]fullerenes have been obtained using electrospray ionization conditions in the positive and negative mode of detection with two different mass spectrometers, a quadrupole ion trap and a Fourier transform ion cyclotron resonance. Radical anions M(●-) and deprotonated molecules [M-H](-) are formed under negative electrospray ionization mass spectrometry conditions, and the collision-induced dissociations of both ionic species have been studied. Either negative odd-electron ions or negative even-electron ions undergo a retro-cycloaddition process forming the corresponding fullerene product ions C(60)(●-) and C(70)(●-). The generation of fullerene radical anions from deprotonated molecules is a new exception of the "even-electron rule." In contrast, the protonated molecules [M + H](+) obtained from the positive mode of detection do not undergo this cycloreversion reaction, and the MS(n) experiment reveals a variety of eliminations of neutral molecules involving different hydrogen shifts and multiple bond cleavages that lead eventually to substituted methanofullerene fragment ions. The observed fragmentations can be correlated with the electronic character of the substituents attached to the heterocyclic moiety. The results obtained from the thermal reactions of these compounds, carried out under different pH conditions, correlate well with those obtained in gas phase. The different behaviors between protonated and unprotonated molecules and ions can be explained assuming that the retro-cycloaddition reaction takes place only when the nitrogen atom of the pyrrolidine ring (the basic center of the molecule) is unprotonated both in gas and condensed phase. The protonation of the NH group inhibits the cycloreversion process, and therefore different fragmentations take place. The detailed mechanisms of the formation and evolution of the intermediate fragments are described.