Experimental and ab-initio calculated vcd spectra of the first OH-stretching overtone of (1R)-(-) and (1S)-(+)-endo-borneol

The near infrared (NIR) absorption and NIR-vibrational circular dichroism (NIR-VCD) spectra of dilute solutions of the two enantiomers of endo-borneol have been measured in the first OH-stretching overtone region (1600–1300 nm). By density functional theory (DFT) we calculate mechanical parameters, i.e. the harmonic mechanical frequency and the anharmonicity constant for the OH stretching, and anharmonic electrical parameters; i.e. the dependence on OH-bond length of atomic polar tensors and atomic axial tensors. We evaluate transition integrals for the calculations of rotational and dipole strengths by Morse anharmonic wavefunctions depending on mechanical harmonic frequencies and mechanical anharmonicity parameters that are calculated ab initio. Experimental and calculated spectra compare quite well and this fact allows us to associate differently signed NIR-VCD features with different conformational states of the OH-bond. Absorption features for the fundamental and for the second overtone of the OH stretching are also compared with experiment

Six-fermion production and Higgs boson physics at future e+e−e^+ e^- colliders

The six-fermion production processes $e^+e^-\to q\bar q l^+ l^-\nu\bar\nu$, with all the lepton flavours and $q=u,d,c,s$, relevant to the study of the intermediate-mass Higgs boson at future $e^+e^-$ linear colliders, are analysed. A Monte Carlo program, taking into account the whole set of tree-level scattering amplitudes and the relevant radiative effects, is developed to provide integrated cross sections and generation of unweighted events. The complete calculation is compared with the available results of real Higgs production, and the opportunities of precision studies with event generation are discussed, demonstrating the relevance of a full six-fermion calculation. Numerical results for integrated cross sections with various kinematical cuts and including radiative effects are given and commented. In the analysis of event samples, several distributions are studied and found to be sensitive to the presence and to the properties of the Higgs boson.Comment: LaTeX, 27 pages, 13 figures included. Minor changes, final version to appear in Eur. Phys. J.

NIR-VCD, vibrational circular dichroism in the near-infrared: Experiments, theory and calculations

The first well documented experiments of Near Infrared Vibrational Circular Dichroism (NIR-VCD) were performed around 1975. We review the thirty year history of NIR-VCD, encompassing both instrumental development and theoretical/computational methods that allow interpretation of experimental spectra, harvesting useful structural information therefrom. We hope to stimulate interest in this still scarcely explored spectroscopy of chiral molecule

PRIVAFRAME: A Frame-Based Knowledge Graph for Sensitive Personal Data

The pervasiveness of dialogue systems and virtual conversation applications raises an important theme: the potential of sharing sensitive information, and the consequent need for protection. To guarantee the subject’s right to privacy, and avoid the leakage of private content, it is important to treat sensitive information. However, any treatment requires firstly to identify sensitive text, and appropriate techniques to do it automatically. The Sensitive Information Detection (SID) task has been explored in the literature in different domains and languages, but there is no common benchmark. Current approaches are mostly based on artificial neural networks (ANN) or transformers based on them. Our research focuses on identifying categories of personal data in informal English sentences, by adopting a new logical-symbolic approach, and eventually hybridising it with ANN models. We present a frame-based knowledge graph built for personal data categories defined in the Data Privacy Vocabulary (DPV). The knowledge graph is designed through the logical composition of already existing frames, and has been evaluated as background knowledge for a SID system against a labeled sensitive information dataset. The accuracy of PRIVAFRAME reached 78%. By comparison, a transformer-based model achieved 12% lower performance on the same dataset. The top-down logical-symbolic frame-based model allows a granular analysis, and does not require a training dataset. These advantages lead us to use it as a layer in a hybrid model, where the logical SID is combined with an ANNs SID tested in a previous study by the authors

Harmonic and Anharmonic Features of IR and NIR Absorption and VCD Spectra of Chiral 4-X-[2.2]Paracyclophanes

The vibrational absorption spectra and vibrational circular dichroism (VCD) spectra of both enantiomers of 4-X-[2.2]paracyclophanes (X ) COOCD3, Cl, I) have been recorded for a few regions in the range of 900- 12000 cm-1. The analysis of the VCD spectra for the two IR regions, 900-1600 cm-1 and 2800-3200 cm-1, is conducted by comparing with DFT calculations of the corresponding spectra; the latter region reveals common motifs of vibrational modes for the three molecules for aliphatic CH stretching fundamentals, whereas in the mid-IR region, one is able to identify specific signatures arising from the substituent groups X. In the CH stretching region between 2900 and 2800 cm-1, we identify and interpret a group of three IR VCD bands due to HCH bending overtone transitions in Fermi resonance with CH stretching fundamental transitions. The analysis of the NIR region between 8000 and 9000 cm-1 for X ) COOCD3 reveals important features of the aromatic CH stretching overtones that are of value since the aromatic CH stretching fundamentals are almost silent. The intensifying of such overtones is attributed to electrical anharmonicity terms, which are evaluated here by ab initio methods and compared with literature data

Dipole and rotational strengths for overtone transitions of a C2-symmetry HCCH molecular fragment using Van Vleck perturbation theory

Contact transformation theory up to second order is employed to treat CH-stretching overtone transitions and to calculate dipole and rotational strengths. A general Hamiltonian describing two interacting CH-stretching oscillators is considered, and the Darling–Dennison resonance is appropriately taken into account. The two CH bonds are supposed to be dissymmetrically disposed, so as to represent a chiral HCCH fragment, endowed with C2 symmetry. Analytical expressions of transition moments and dipole and rotational strengths are given in the hypothesis of general electric and magnetic dipole moments with quadratic dependence on coordinates and momenta. Dipole and rotational strengths are then calculated together with frequencies for the fundamental and first three overtone regions in the simplifying hypothesis of the valence optical approach on the coupled-oscillator framework. Simplified analytical expressions thereof in the relevant parameters are presented

Lymphocyte Subsets and Inflammatory Cytokines of Monoclonal Gammopathy of Undetermined Significance and Multiple Myeloma

Almost all multiple myeloma (MM) cases have been demonstrated to be linked to earlier monoclonal gammopathy of undetermined significance (MGUS). Nevertheless, there are no identified characteristics in the diagnosis of MGUS that have been helpful in differentiating subjects whose cancer may progress to a malignant situation. Regarding malignancy, the role of lymphocyte subsets and cytokines at the beginning of neoplastic diseases is now incontestable. In this review, we have concentrated our attention on the equilibrium between the diverse lymphocyte subsets and the cytokine system and summarized the current state of knowledge, providing an overview of the condition of the entire system in MGUS and MM. In an age where the therapy of neoplastic monoclonal gammopathies largely relies on drugs capable of acting on the immune system (immunomodulants, immunological checkpoint inhibitors, CAR-T), detailed knowledge of the the differences existing in benign and neoplastic forms of gammopathy is the main foundation for the adequate and optimal use of new drugs

Vibrational Excitons in CH-Stretching Fundamental and Overtone Vibrational Circular Dichroism Spectra

A set of vibrational circular dichroism (VCD) spectra in the CH-stretching fundamental region for about twenty compounds belonging to the class of essential oils was empirically analyzed by the use of a sort of vibrational exciton mechanism, involving three centers. Through a general formula applicable to many coupled dipole oscillators, the rotational strengths of the previously identified vibrational excitons are evaluated. The results are then critically reviewed by the use of recent ab initio methodology, as applied to selected molecules of the original set. Further insight is gained by model calculations adding up the contribution of the coupling between electric dipole moments associated with normal mode behavior and that of the polarizability from polarizable groups. The former part is responsible for the excitonic behavior of the VCD spectra. For the same selected molecules we have also investigated whether some excitonic behavior is taking place in the second overtone region, and have concluded that this is not the case