Applications of Raman spectroscopy to gemology

Being nondestructive and requiring short measurement times, a low amount of material, and no sample preparation, Raman spectroscopy is used for routine investigation in the study of gemstone inclusions and treatments and for the characterization of mounted gems. In this work, a review of the use of laboratory Raman and micro-Raman spectrometers and of portable Raman systems in the gemology field is given, focusing on gem identification and on the evaluation of the composition, provenance, and genesis of gems. Many examples are shown of the use of Raman spectroscopy as a tool for the identification of imitations, synthetic gems, and enhancement treatments in natural gemstones. Some recent developments are described, with particular attention being given to the semiprecious stone jade and to two important organic materials used in jewelry, i.e., pearls and corals.     

Thorough evaluation of the validity of conventional enantio-gas chromatography in the analysis of volatile chiral compounds in mandarin essential oil: A comparative investigation with multidimensional gas chromatography

The present research is focused on the determination of the enantiomeric distribution of chiral compounds, contained in mandarin essential oils, by means of conventional chiral gas chromatography with flame ionization detection (enantio-GC-FID); the results attained were compared with those derived from heart-cutting multidimensional GC-mass spectrometry (MDGC/MS), to evaluate the reliability of the monodimensional technique as a tool for quality control. The Deans-switch MDGC system was equipped with two GC ovens, which were connected via a heated transfer line, a flame ionization detector (FID1) in the first dimension and a quadrupole MS as second-dimension detector. The a priori knowledge of potential co-elutions concerning target compounds (an enantiomer and an interfering compound), when using enantio-GC-FID, could enable the use of corrected enantiomer excess values. Correction factors could be calculated through a preliminary GC-FID analysis (using an apolar column), considering the peak areas of the known interferences. The method used for the calculation of a so-called “coelution correction factor” is described, along with some examples.     

On Two Superintegrable Nonlinear Oscillators in N Dimensions

We consider the classical superintegrable Hamiltonian system given by

The Airy transform and associated polynomials

The Airy transform is an ideally suited tool to treat problems in classical and quantum optics. Even though the relevant mathematical aspects have been thoroughly investigated, the possibilities it offers are wide and some features, such as the link with special functions and polynomials, still contain unexplored aspects. In this note we will show that the so called Airy polynomials are essentially the third order Hermite polynomials. We will also prove that this identification opens the possibility of developing new conjectures on the properties of this family of polynomials.     

Interpolation by neural network operators activated by ramp functions

In this paper, a family of interpolation neural network operators are introduced. Here, ramp functions as well as sigmoidal functions generated by central B-splines are considered as activation functions. The interpolation properties of these operators are proved, together with a uniform approximation theorem with order, for continuous functions defined on bounded intervals. The relations with the theory of neural networks and with the theory of the generalized sampling operators are discussed.     

Incompatibilism and the logic of transfer

Modal arguments for incompatibility of freedom and determinism are typically based on the “transfer principle” for inability to act otherwise (Beta). The principle of agglomerativity (closure under conjunction introduction) is derivable from Beta. The most convincing counterexample to Beta is based on the denial of Agglomeration. The defender of the modal argument has two ways to block counterexamples to Beta: (i) use a notion of inability to act otherwise which is immune to the counterexample to agglomerativity; (ii) replace Beta with a logically stronger principle Beta 2. I argue that the second strategy fails because the strengthened principle and Agglomeration together entail Beta. So this strategy makes sense only if Beta 2 is applied without Agglomeration. But if Beta 2 is used without Agglomeration, then the incompatibilist will undercut the rationale for the premise of his argument. I illustrate this point with the analysis of Warfield (1996) and his use of Beta 2 in the so called direct argument for incompatibilism.     

Periodic and Non-Periodic Oscillations of a Class of Hysteretic Two Degree of Freedom Systems

The equations governing the response of hysteretic systems to sinusoidal forces, which are memory dependent in the classical phase space, can be given as a vector field over a suitable phase space with increased dimension. Hence, the stationary response can be studied with the aids of classical tools of nonlinear dynamics, as for example the Poincaré map. The particular system studied in the paper, based on hysteretic Masing rules, allows the reduction of the dimension of the phase space and the implementation of efficient algorithms. The paper summarises results on one degree of freedom systems and concentrates on a two degree of freedom system as the prototype of many degree of freedom systems. This system has been chosen to be in 1:3 internal resonance situation. Depending on the energy dissipation of the elements restoring force, the response may be more or less complex. The periodic response, described by frequency response curves for various levels of excitation intensity, is highly complex. The coupling produces a strong modification of the response around the first mode resonance, whereas it is negligible around the second mode. Quasi-periodic motion starts bifurcating for sufficiently high values of the excitation intensity; windows of periodic motions are embedded in the dominion of the quasi-periodic motion, as consequence of a locking frequency phenomenon.     

Chemical composition and antioxidant activity of essential oil from aerial parts of Teucrium flavum L. subsp. flavum growing spontaneously in Tunisia

The objectives of this study were to chemically characterise and evaluate the antioxidant potential of the essential oil from Teucrium flavum L. subsp. flavum growing spontaneously in Tunisia. The volatile oil was extracted by hydrodistillation of the aerial parts in a Clevenger type apparatus. Forty constituents were identified via GC and GC-MS analysis. β-caryophyllene (32.5%) and α-humulene (17.8%) were the most abundant components. The evaluation of free radical scavenging activity using stable DPPH free radical showed that the volatile oil exhibits a moderate antioxidant activity and reduces DPPH to 50% at EC₅₀ value of 1230 μg mL^? 1.     

On the Logical Status of the Virtual Work Law

The law of virtual work (VWL) is probably the first law in the history of mechanics; it is previous to the one on the lever, though not completely distinct from it. Here I will discuss the logical status of VWL, that is whether it is an autonomous principle or a theorem of some sort of mechanics. The problem is complicated by the fact that up to now no universally recognised expression has been accepted for it. From this article the problematical nature of VWL demonstrability is quite clear when the mechanics does not characterise completely the constraints. Italian schools in the XVIII century, even if we do not take Lagrange into consideration, had an important role, both in the development of VWL and in the discussion of its role.     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.