Relaxation processes of the liquid crystal ME6N in the isotropic phase studied by Raman scattering experiments

We have investigated the Raman profiles of the nu(C[Triple Bond]N) and nu(C=O) vibrational modes of the nematic liquid crystal ME6N (4-cyanophenyl-4(')-hexylbenzoate) in the isotropic phase at different temperatures and used them as probes of the dynamics and structural organization of this liquid. The vibrational time correlation functions of the nu(C[Triple Bond]N) mode, rather adequately interpreted within the assumption of exponential modulation function (the Kubo-Rothschild theory), indicate that the system experiences an intermediate dynamical regime that gets only slightly faster with increasing temperature. However, this theory fails in predicting the non-exponential behavior that the time correlation functions manifest in the long time range (t>3 ps). For this reason we have additionally approached the interpretation of vibrational correlation functions in terms of the theory formulated by Rothschild and co-workers for locally structured liquids. The application of this theory reveals that the molecular dynamics in this liquid crystal in the isotropic phase is that deriving from a distribution of differently sized clusters, which narrows as the temperature increases. Even at the highest temperature reached in this study (87 degrees C above the nematic-isotropic transition), the liquid has not yet achieved the structure of the simple liquid and the dynamics has not reached the limit of the single channel process. The vibrational and orientational relaxations occur in very different time scales. The temperature independence of the orientational dynamics in the whole range from 55 degrees C to 135 degrees C has been referred to the nonhydrodynamic behavior of the system, arising when local pseudonematic structures persist for times longer than the orientational relaxation. The occurrence of the process of resonant vibrational energy transfer between the C=O groups of adjacent molecules has been revealed in the isotropic phase by a slightly positive Raman noncoincidence effect in the band associated with the nu(C=O) mode. A qualitative interpretation is tentatively given in terms of partial cancellation of contributions deriving from structures having opposite orientations of their C=O groups.     

Study of ruthenium(II) complexes with anticancer drugs as ligands. Design of metal-based phototherapeutic agents

The reaction of trans-[RuCl(2)(PPh(3))(3)] (Ph = C(6)H(5)) with 2-thio-1,3-pyrimidine (HTPYM) and 6-thiopurines (TPs) produced mainly crystalline solids that consist of cis,cis,trans-[Ru(PPh(3))(2)(N,S-TPYM)(2)] (1) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-TPs)(2)]X(2) (X = Cl(-), CF(3)SO(3)(-)). In the case of TPs, other coordination isomers have never been isolated and reported. Instead, the mother liquor obtained after filtration of 1 produced red single crystals of trans,cis,cis-[Ru(PPh(3))(2)(N,S-TPYM)(2)].2H(3)O(+).2Cl(-) (2.2H(3)O(+).2Cl(-)). Selected ruthenium(II)-thiobase complexes were studied for their structural, reactivity, spectroscopic, redox, and cytotoxic properties. Single crystals of 1 contain thiopyrimidinato anions chelated to the metal center via N and S. The Ru[bond]N bonds are significantly elongated for 1 [2.122(2) and 2.167(2) A] with respect to 2 [2.063(3) A] because of the trans influence from PPh(3). The coordination pseudo-octahedron for 2 is significantly elongated at the apical sites (PPh(3) ligands). Solutions of cis,cis,trans isomers in air are stable for weeks, whereas those of 2 turn green within 24 h, in agreement with the respective redox potentials. cis,cis,trans- and trans,cis,cis-[Ru(PH(3))(2)(N,S-TPYM)(2)], as optimized through the DFT methods at the Becke3LYP level are in good agreement with experimental geometrical parameters (1 and 2), with cis,cis,trans being more stable than trans,cis,cis by 3.88 kcal. The trend is confirmed by molecular modeling based on semiempirical (ZINDO/1) and molecular mechanics (MM) methods. Cytotoxic activity measurements for cis,cis,trans-[Ru(PPh(3))(N-THZ)(N(7),S -H(2)TP)(2)]Cl(2) (4) (THZ = thiazole, H(2)TP = 6-thiopurine) and cis,cis,trans-[Ru(PPh(3))(2)(N(7),S-HTPR)2]Cl(2) (5) (HTPR = 6-thiopurine riboside) against ovarian cancer cells A2780/S gave IC(50) values of 17 +/- 1 and 29 +/- 9 microM, respectively. Furthermore, the spectral analysis of HTPYM, TPs, and their Ru(II) complexes in solution shows that intense absorptions occur in the UVA/vis region of light, whereas standard nucleobases absorb in the UVB region.     

New antiproliferative 14,15-secopregnane glycosides from Solenostemma argel

Eight new 14,15-secopregnane glycosides, namely argelosides C-J, possessing two ketal functions involved in three five-membered rings, have been isolated from the hairy seeds of Solenostemma argel. Their structures have been established by MS and NMR experiments, combined with quantum mechanical calculations of the ¹³C chemical shifts for the interpretation of the experimental data. On the basis of the obtained results, the structures of argelosides A and B have been revised. Additionally, the effect of these compounds on the VEGF-induced in Kaposi's sarcoma cell proliferation was evaluated. Results indicated that all the compounds reduced the cell proliferation in a dose-dependent manner.     

Osteoarthritis subjects have differentiated lower extremity thermal skin response after the concurrent acute training session

Journal of Thermal Analysis and Calorimetry - This study investigated the thermal skin (Tsk) response of lower limbs in older adults with or without osteoarthritis before and after a concurrent...     

Crosslinked Hyaluronic Acid with Liposomes and Crocin Confers Cytoprotection in an Experimental Model of Dry Eye

Dry eye disease (DED) is a multifactorial condition caused by tear deficiency and accompanied by ocular surface damage. Recent data support a key role of oxidative and inflammatory processes in the pathogenesis of DED. Hyaluronic acid (HA) is widely used in artificial tears to treat DED by improving ocular hydration and reducing surface friction. Crocin (Cr), the main constituent of saffron, is a renowned compound that exhibits potent antioxidant and anti-inflammatory effects. The present study was undertaken to assess the viscosity and muco-adhesiveness of a photoactivated formulation with crosslinked HA (cHA), Cr, and liposomes (cHA-Cr-L). Our aim was also to evaluate whether cHA-Cr-L may exert cytoprotective effects against oxidative and inflammatory processes in human corneal epithelial cells (HCECs). Viscosity was measured using a rotational rheometer, and then the muco-adhesiveness was evaluated. Under hyperosmolarity (450 mOsm), the HCECs were treated with cHA-Cr-L. Interleukin-1β (IL-1β) and tumor necrosis factor α (TNFα) were quantified by quantitative real-time polymerase chain reaction (RT-qPCR). The levels of reactive oxygen species (ROS) were measured using the DCF assay. The combined action of cHA-Cr-L produced a higher viscosity and muco-adhesiveness compared to the control. The anti-inflammatory effect of cHA-Cr-L was achieved through a significant reduction of IL-1β and TNFα (p < 0.001). The results also showed that cHA-Cr-L reduces ROS production under conditions of hyperosmolarity (p < 0.001). We conclude that cHA-Cr-L has potential as a therapeutic agent in DED, which should be further investigated.     

13C direct detected experiments: optimization for paramagnetic signals

To optimize 13C direct detected experiments for the observation of signals close to a paramagnetic center, we have assessed the sensitivity of different sequences based on CO-Cali coherence transfer. Features of CACO experiments were tested for Calbindin D9k, in which one of the two native Ca2+ ions is replaced by the paramagnetic Ce3+ ion. We have studied the comparison of single vs multiple quantum coherence transfer evolution as well as the influence of in-phase vs anti-phase detection of 13CO signals and finally the comparison of a coherence transfer step based on a CyO in plane with respect to a Cy ali in plane. The acquisition of the anti-phase component of the signal, accomplished by the removal of the last refocusing steps, allowed the identification of some signals unobserved with other pathways. The structural dependency of paramagnetism-induced nuclear relaxation is such that the identification of the most suitable coherence transfer pathway is not known "a priori" but it is driven by the relative proximity of Cali and CO to the paramagnetic center.     

Ring-closing olefin metathesis of 2,2'-divinylbiphenyls: a novel and general approach to phenanthrenes

[reaction: see text] The ring-closing olefin metathesis (RCM) of 2,2'-divinylbiphenyls, using a second-generation RCM ruthenium-based catalyst, leads to differently substituted phenanthrenes in quantitative yield under very mild reaction conditions, independent of both nature and position of the groups present on the biphenyl moiety.     

Protein hydration and location of water molecules in oxidized horse heart cytochrome c by (1)H NMR

The hydration properties of the oxidized form of horse heart cytochrome c have been studied by (1)H NMR spectroscopy. Two-dimensional, homonuclear ePHOGSY-NOESY experiments are used to map water-protein interactions. The detected NOEs reveal interactions between nonexchangeable protein protons and both water protons and labile protein protons which exchange with water protons. Among the many water molecules apparent in the X-ray structure, three have been identified with a residence time longer than 300 ps. One of them is located inside the distal heme cavity, in the deepest part of a hydration pathway extending toward the surface. The identification of hydrophilic regions and detection of three long-lived water molecules settles some ambiguities and provides a better representation of the water-protein interactions in oxidized cytochrome c.