Structure determination of neutral MgO clusters--hexagonal nanotubes and cages

Structural information for neutral magnesium oxide clusters has been obtained by a comparison of their experimental vibrational spectra with predictions from theory. (MgO)(n) clusters with n = 3-16 have been studied in the gas phase with a tunable IR-UV two-color ionization scheme and size-selective infrared spectra have been measured. These IR spectra are compared to the calculated spectra of the global minimum structures predicted by a hybrid ab initio genetic algorithm. The comparison shows clear evidence that clusters of the composition (MgO)(3k) (k = 1-5) form hexagonal tubes, which confirm previous theoretical predictions. For the intermediate sizes (n≠ 3k) cage-like structures containing hexagonal (MgO)(3) rings are identified. Except for the cubic (MgO)(4) no evidence for bulk like structures is found.     

Identification of naphthoylindoles acting on cannabinoid receptors based on their fragmentation patterns under ESI-QTOFMS

'Herbal highs' have been advertised as legal and natural substitutes to cannabis, but a detailed examination of these products has revealed that the herbal matrix is laced with synthetic substances that mimic the effects of marijuana. Producers select the ingredients based on the results of scientific studies on the affinities of different chemicals to cannabinoid receptors. Naphthoylindoles have turned out to be the most popular class of substances identified in the products. Legal actions taken in order to tackle the problem of uncontrolled access to one substance have usually resulted in the marketing of derivatives or analogues. In the study, the mass spectral behavior of twelve synthetic cannabinoids from the naphthoylindole family under electrospray ionization (ESI) was investigated. LC-QTOFMS experiments were performed in three modes (low fragmentor voltage, high fragmentor voltage with/without collision energy), and they enabled the identification of protonated molecules and main ions. A general fragmentation pattern under this ionization method was proposed, and mechanisms of ion formation were discussed. The developed procedure allowed the determination of substituent groups of the core naphthoylindole structure and distinction between positional isomers. The obtained results were used for the prediction of the ESI-MS spectra for many naphthoylindoles with a high affinity to cannabinoid receptors. Similarities and differences between ESI-MS and electron impact-MS spectra of naphthoylindoles were discussed. The developed identification process was presented on an example of an analysis of an unknown herbal material, in which JWH-007 was finally identified. Knowledge of the fragmentation mechanisms of naphthoylindoles could also be used by other researchers for identification of unknown substances in this chemical family.     

Voice gender differences and separation of simultaneous talkers in cochlear implant users with residual hearing

Perception of a target voice in the presence of a competing talker, of same or different gender as the target, was investigated in cochlear implant users, in implant-alone and bimodal (acoustic hearing in the non-implanted ear) conditions. Recordings of two male and two female talkers acted as targets and maskers, to investigate whether bimodal benefit increased for different compared to same gender target/maskers due to increased ability to perceive and utilize fundamental frequency and spectral-shape differences. In both listening conditions participants showed benefit of target/masker gender difference. There was an overall bimodal benefit, which was independent of target/masker gender difference.     

Give or Take: Effects of Electron-Accepting/-Withdrawing Groups in Red-Fluorescent BODIPY Molecular Rotors

Mapping microviscosity, temperature, and polarity in biosystems is an important capability that can aid in disease detection. This can be achieved using fluorescent sensors based on a green-emitting BODIPY group. However, red fluorescent sensors are desired for convenient imaging of biological samples. It is known that phenyl substituents in the β position of the BODIPY core can shift the fluorescence spectra to longer wavelengths. In this research, we report how electron-withdrawing (EWG) and -donating (EDG) groups can change the spectral and sensory properties of β-phenyl-substituted BODIPYs. We present a trifluoromethyl-substituted (EWG) conjugate with moderate temperature sensing properties and a methoxy-substituted (EDG) molecule that could be used as a lifetime-based polarity probe. In this study, we utilise experimental results of steady-state and time-resolved fluorescence, as well as quantum chemical calculations using density functional theory (DFT). We also explain how the energy barrier height (Ea) for non-radiative relaxation affects the probe’s sensitivity to temperature and viscosity and provide appropriate Ea ranges for the best possible sensitivity to viscosity and temperature.     

The Effect of Antiretroviral Therapy on SIRT1, SIRT3 and SIRT6 Expression in HIV-Infected Patients

Human Immunodeficiency Virus (HIV) infection and the chronic use of combined antiretroviral therapy (cART) may affect the occurrence of certain disturbances in the body. There is growing interest in sirtuins–enzymes involved in the regulation of many metabolic processes in the organism and in the pathogenesis of many diseases which also exhibit potential antiviral activity. The aim of the study was to investigate the connection of cART to the expression of Sirtuin 1 (SIRT1), Sirtuin 3 (SIRT3) and Sirtuin 6 (SIRT6) in HIV-infected men. The plasma levels of sirtuins were measured before and one year after cART, and related to HIV viral load, lymphocytes T CD4+ and CD8+ count as well as the applied cART. The levels of sirtuins in plasma were measured in HIV-infected patients (n = 53) and the control group (n = 35) by immunoassay methods. There were statistically significant (p < 0.05) differences between SIRT6 in the HIV-infected patients before therapy and in the subgroups, depending on the count of lymphocytes T CD8+. There were significant differences in the levels of SIRT1 depending on the applied treatment regimen. The obtained results indicate the most significant changes in the expression of SIRT6 in the course of HIV infection and suggest an influence of the type of cART on the level of SIRT1, which indicates its important role in the course of HIV.     

Poly(vinylbenzyl Pyridinium Salts) as Novel Sorbents for Hazardous Metals Ions Removal

Novel efficient complexing resins—poly(vinylbenzyl pyridinium salts) fabricated through poly(vinylbenzyl halogene-co-divinylbenzene) quaternization of N-decyloxy-1-(pyridin-3-yl)ethaneimine and N-decyloxy-1-(pyridin-4-yl)ethaneimine—were tested as adsorbents of Pb(II), Cd(II), Cu(II), Zn(II), and Ni(II) from aqueous solutions. The structure of these materials was established by ¹³C CP-MAS NMR, X-ray photoelectron spectroscopy, elemental analysis, and Fourier transform infrared spectroscopy, as well as thermogravimetric and differential thermal analyses. The textural properties were determined using scanning electron microscopy and low-temperature N₂ sorption. Based on the conducted sorption studies, it was shown that the uptake behavior of the metal ions towards novel resins depended on the type of functionalities, contact time, pH, metal concentrations, and the resin dosage. The Langmuir model was investigated to be the best one for fitting isothermal adsorption equilibrium data, and the corresponding adsorption capacities were predicted to be 296.4, 201.8, 83.8, 38.1, and 39.3 mg/g for Pb(II), Zn(II), Cd(II), Cu(II), and Ni(II), respectively. These results confirmed that owing to the presence of the functional pyridinium groups, the resins demonstrated proficient metal ion removal capacities. Furthermore, VBBr-D4EI could be successfully used for the selective uptake of Pb(II) from wastewater. It was also shown that the novel resins can be regenerated without significant loss of their sorption capacity.     

Coordination chemistry of H-spirophosphorane ligands towards pentacarbonylchlororhenium(I) – synthesis,structure and catalytic activity of complexes

Synthesis of a group of carbonyl rhenium coordination compounds with hydrospirophosphorane ligands was carried out and described. Different symmetrical HP(OCH₂CH₂NH)₂ L1 , HP(OCH₂CMe₂NH)₂ L2 , HP(OC₆H₄NH)₂ L3 , and unsymmetrical ligands HP (OCMe₂CMe₂O)(OC₆H₄NH) L4 were found to coordinate to the rhenium center as bidentate P,N donor ligands yielding fac-[ReCl (CO)₃ Ln ], where n = 1 – 4. Furthermore, monodentate coordination was also observed in some cases, as was clearly presented in the case of [ReCl(CO)₂( L4- κ²P,N)( L4- κP)] complex. All of the complexes were characterized using optical spectroscopy. Single-crystalX-ray diffraction was also performed in the case of fac-[ReCl(CO)₃ L3 ], fac-[ReCl(CO)₃ L4 ], [Re(CO)₂( L2 )₂]Cl and [ReCl (CO)₂( L4- κ²P,N)( L4- κP)] samples. Complexes [ReCl(CO)₃ L3 ] and [ReCl (CO)₃ L4 ], both bearing rings of conjugated double bonds within hydrospirophosphorane ligands, exhibited luminescence. Catalytic properties of rhenium complexes were assessed using the representative fac-[ReCl (CO)₃ L2 ] complex in the dimerization reaction of terminal alkynes. An efficient and selective procedure for synthesis of the E - enynes was developed. Coupling of (2-chlorophenyl)acetylene was mediated by [ReCl (CO)₃ L2 ]/TBAF system with a 100% conversion rate. Different substituents within aromatic alkynes were tolerated and the resulting products were dependent on the nature of the substituents.     

Slice modules over minimal 2-fundamental algebras

We consider a class of algebras whose Auslander-Reiten quivers have starting components that are not generalized standard. For these components we introduce a generalization of a slice and show that only in finitely many cases (up to isomorphism) a slice module is a tilting module. The first named author was supported by the Polish Scientific Grant KBN No 1 P03A 018 27