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

Sexual Functioning and Opioid Maintenance Treatment in Women. Results From a Large Multicentre Study

Opioid maintenance treatment (OMT) is the most widespread therapy for both females and males opioid addicts. While many studies have evaluated the OMT impact on men’s sexuality, the data collected about the change in women’s sexual functioning is still limited despite the fact that it is now well-known that opioids - both endogenous and exogenous - affect the endocrine system and play an important role in sexual functioning. The present study aims to determine how OMT with buprenorphine (BUP) or methadone (MTD) affects sexual health in women; examining also any possible emerging correlation between sexual dysfunction (SD), type of opioid and patients’ mental health. This multi-center study case recruited 258 female volunteers attending Italian public Addiction Outpatients Centers that were stabilized with OMT for at least 3 months. SD was assessed with the Arizona Sexual Experience Scale. The twelve-item General Health Questionnaire was used to assess participants’ mental health conditions. The results show that 56.6% of women receiving OMT for at least 3 months presented SD without significant differences between MTD e BUP groups. The majority of the subjects with SD have a poorer quality of intimate relationships and worse mental health than the average. To the best of our knowledge, the present study is the largest report on the presence of SDs in women as a side effects of MTD and BUP used in OMT. Since SDs cause difficulties in intimate relationships, lower patients’ quality of life and interfere with OMT beneficial outcomes, we recommend that women undertaking an opioid therapy have routine screening for SD and we highlight the importance to better examine opioid-endocrine interactions in future studies in order to provide alternative potential treatments such as the choice of opioid, opioid dose reduction and hormone supplementation

BMS flux algebra in celestial holography

Starting from gravity in asymptotically flat spacetime, the BMS momentum fluxes are constructed. These are non-local expressions of the solution space living on the celestial Riemann surface. They transform in the coadjoint representation of the extended BMS group and correspond to Virasoro primaries under the action of bulk superrotations. The relation between the BMS momentum fluxes and celestial CFT operators is then established: the supermomentum flux is related to the supertranslation operator and the super angular momentum flux is linked to the stress-energy tensor of the celestial CFT. The transformation under the action of asymptotic symmetries and the OPEs of the celestial CFT currents are deduced from the BMS flux algebra

Loop-corrected subleading soft theorem and the celestial stress tensor

We demonstrate that the one-loop exact subleading soft graviton theorem automatically follows from conservation of the BMS charges, provided that the hard and soft fluxes separately represent the extended BMS algebra at null infinity. This confirms that superrotations are genuine symmetries of the gravitational S-matrix beyond the semiclassical regime. In contrast with a previous proposal, the celestial stress tensor accounting for the one-loop corrections follows from the gravitational phase space analysis and does not require the addition of divergent counterterms. Moreover, we show that the symplectic form on the radiative phase space factorises into hard and soft sectors, and that the resulting canonical generators precisely coincide with the correct BMS fluxes

Circular Dichroism Spectra (350-185 nm) of a New Series of 4-Substituted [2.2] Paracyclophanes: a Quantitative Analysis within the De Voe Polarizability Model

The CD spectra of a new series of 4-substituted [2.2]paracyclophanes 1b- e have been measured down to 185 nm. Polarizability calculations within the DeVoe model satisfactorily reproduce the CD features over all the spectral range. In addition, the analysis of the complete CD spectrum allowed a phenomenological interpretation of the dependence of the sign of [α](D) on the nature of the substituents, at least for X=F, OH, I