A mode coupling theory description of the short- and long-time dynamics of nematogens in the isotropic phase

Optical heterodyne-detected optical Kerr effect (OHD-OKE) experimental data are pre-sented on nematogens 4-(trans-4-n-octylcyclohexyl)isothiocyanatobenzene (8-CHBT), and 4-(4-pentyl-cyclohexyl)-benzonitrile (5-PCH) in the isotropic phase. The 8-CHBT and 5-PCH data and previously published data on 4-pentyl-4-biphenylcarbonitrile (5-CB) are analyzed using a modification of a schematic mode coupling theory (MCT) that has been successful in describing the dynamics of supercooled liquids. At long time, the OHD-OKE data (orientational relaxation) are well described with the standard Landau-de Gennes (LdG) theory. The data decay as a single exponential. The decay time diverges as the isotropic to nematic phase transition is approached from above. Previously there has been no theory that can describe the complex dynamics that occur at times short compared to the LdG exponential decay. Earlier, it has been noted that the short-time nematogen dynamics, which consist of several power laws, have a functional form identical to that observed for the short time behavior of the orientational relaxation of supercooled liquids. The temperature-dependent orientational dynamics of supercooled liquids have recently been successfully described using a schematic mode coupling theory. The schematic MCT theory that fits the supercooled liquid data does not reproduce the nematogen data within experimental error. The similarities of the nematogen data to the supercooled liquid data are the motivation for applying a modification of the successful MCT theory to nematogen dynamics in the isotropic phase. The results presented below show that the new schematic MCT theory does an excellent job of reproducing the nematogen isotropic phase OHD-OKE data on all time scales and at all temperatures.     

Synthesis, characterization, DNA-binding, photocleavage, cytotoxicity and docking studies of Co(III) mixed ligand complexes

A new ligand, (2-ethoxy-6-(1H imadazo[4,5-f][1,10]phenanthroline-2-yl)phenol) (HEPIP) and its three Co(III) complexes [Co(phen)₂(HEPIP)](ClO₄)₃ (1), [Co(bpy)₂(HEPIP)](ClO₄)₃ (2) and [Co(dmb)₂(HEPIP)](ClO₄)₃ (3) have been synthesized and characterized. All three Co(III) complexes exhibited antitumor activity against four human tumor cell lines. The interaction of these complexes with calf thymus DNA was studied by absorption and emission spectroscopy, viscosity measurements and DNA cleavage assays. The DNA-binding constants of complexes 1, 2 and 3 were determined as 6.13 × 10⁵, 4.46 × 10⁵ and 3.72 × 10⁵ M^?1, respectively. The complexes appear to interact with DNA through intercalation. Studies on the mechanism of photocleavage indicated that both superoxide anion radical and singlet oxygen may play an important role.     

Testing the core/shell model of nanoconfined water in reverse micelles using linear and nonlinear IR spectroscopy

A core/shell model has often been used to describe water confined to the interior of reverse micelles. The validity of this model for water encapsulated in AOT/isooctane reverse micelles ranging in diameter from 1.7 to 28 nm (w0 = 2-60) and bulk water is investigated using four experimental observables: the hydroxyl stretch absorption spectra, vibrational population relaxation times, orientational relaxation rates, and spectral diffusion dynamics. The time dependent observables are measured with ultrafast infrared spectrally resolved pump-probe and vibrational echo spectroscopies. Major progressive changes appear in all observables as the system moves from bulk water to the smallest water nanopool, w0 = 2. The dynamics are readily distinguishable for reverse micelle sizes smaller than 7 nm in diameter (w0 = 20) compared to the response of bulk water. The results also demonstrate that the size dependent absorption spectra and population relaxation times can be quantitatively predicted using a core-shell model in which the properties of the core (interior of the nanopool) are taken to be those of bulk water and the properties of the shell (water associated with the headgroups) are taken to be those of w0 = 2. A weighted sum of the core and shell components reproduces the size dependent spectra and the nonexponential population relaxation dynamics. However, the same model does not reproduce the spectral diffusion and the orientational relaxation experiments. It is proposed that, when hydrogen bond structural rearrangement is involved (orientational relaxation and spectral diffusion), dynamical coupling between the shell and the core cause the water nanopool to display more homogeneous dynamics. Therefore, the absorption spectra and vibrational lifetime decays can discern different hydrogen bonding environments whereas orientational and spectral diffusion correlation functions predict that the dynamics are size dependent but not as strongly spatially dependent within a reverse micelle.     

Four novel spirooxazacamphorsultam derivatives

The chiral compounds (6aS,9S,10aR)‐11,11‐dimethyl‐5,5‐dioxo‐2,3,8,9‐tetrahydro‐6H‐6a,9‐methanooxazaolo[2,3‐i][2,1]benzisothiazol‐10(7H)‐one, C₁₂H₁₇NO₄S, (1), (7aS,10S,11aR)‐12,12‐dimethyl‐6,6‐dioxo‐3,4,9,10‐tetrahydro‐7H‐7a,10‐methano‐2H‐1,3‐oxazino[2,3‐i][2,1]benzisothiazol‐11(8H)‐one, C₁₃H₁₉NO₄S, (2), (6aS,9S,10R,10aR)‐11,11‐dimethyl‐5,5‐dioxo‐2,3,7,8,9,10‐hexahydro‐6H‐6a,9‐methanooxazolo[2,3‐i][2,1]benzisothiazol‐10‐ol, C₁₂H₁₉NO₄S, (3), and (7aS,10S,11R,11aR)‐12,12‐dimethyl‐6,6‐dioxo‐3,4,8,9,10,11‐hexahydro‐7H‐7a‐methano‐2H‐[1,3]oxazino[2,3‐i][2,1]benzisothiazol‐11‐ol, C₁₃H₂₁NO₄S, (4), consist of a camphor core with a five‐membered spirosultaoxazolidine or six‐membered spirosultaoxazine, as both their keto and hydroxy derivatives. In each structure, the molecules are linked via hydrogen bonding to the sulfonyl O atoms, forming chains in the unit‐cell b‐axis direction. The chains interconnect via weak C—H...O interactions. The keto compounds have very similar packing but represent the highest melting [507–508 K for (1)] and lowest melting [457–458 K for (2)] solids.     

Effect of Electron Beam Irradiation on the Kinetics of Non-isothermal Crystallization of Nylon 66

The non-isothermal crystallization kinetics was studied by differential scanning calorimetric analysis on nylon 66 and e-beam irradiated nylon 66 at different cooling rates. The Modified Avrami equation, the Ozawa equation and the Combined Avrami-Ozawa equation were applied to study the kinetics of non-isothermal crystallization of nylon 66. The crystallization behavior of pristine nylon 66 polymer was compared with that of e-beam irradiated nylon 66 and observed that the kinetics of non-isothermal crystallization of nylon66 was affected largely upon e-beam irradiation. E-beam irradiation not only decreased the crystallization temperature of nylon 66, but influenced the mechanism of nucleation and crystal growth and reduced the overall crystallization rate of nylon 66 also. The crystallization activation energy calculated by the Kissinger method for irradiated nylon 66 was lower than that of pristine nylon 66.     

Dynamics of water probed with vibrational echo correlation spectroscopy

Vibrational echo correlation spectroscopy experiments on the OD stretch of dilute HOD in H(2)O are used to probe the structural dynamics of water. A method is demonstrated for combining correlation spectra taken with different infrared pulse bandwidths (pulse durations), making it possible to use data collected from many experiments in which the laser pulse properties are not identical. Accurate measurements of the OD stretch anharmonicity (162 cm(-1)) are presented and used in the data analysis. In addition, the recent accurate determination of the OD vibrational lifetime (1.45 ps) and the time scale for the production of vibrational relaxation induced broken hydrogen bond "photoproducts" ( approximately 2 ps) aid in the data analysis. The data are analyzed using time dependent diagrammatic perturbation theory to obtain the frequency time correlation function (FTCF). The results are an improved FTCF compared to that obtained previously with vibrational echo correlation spectroscopy. The experimental data and the experimentally determined FTCF are compared to calculations that employ a polarizable water model (SPC-FQ) to calculate the FTCF. The SPC-FQ derived FTCF is much closer to the experimental results than previously tested nonpolarizable water models which are also presented for comparison.     

Dynamics of hemoglobin in human erythrocytes and in solution: influence of viscosity studied by ultrafast vibrational echo experiments

Ultrafast spectrally resolved stimulated vibrational echo experiments are used to measure the vibrational dephasing of the CO stretching mode of hemoglobin-CO (HbCO) inside living human erythrocytes (red blood cells), in liquid solutions, and in a glassy matrix. A method is presented to overcome the adverse impact on the vibrational echo signal from the strong light scattering caused by the cells. The results from the cytoplasmic HbCO are compared to experiments on aqueous HbCO samples prepared in different buffers, solutions containing low and high concentrations of glycerol, and in a solid trehalose matrix. Measurements are also presented that provide an accurate determination of the viscosity at the very high Hb concentration that is found inside the cells. It is demonstrated that the dynamics of the protein, as sensed by the CO ligand, are the same inside the erythrocytes and in aqueous solution and are independent of the viscosity. In solutions that are predominantly glycerol, the dynamics are modified somewhat but are still independent of viscosity. The experiments in trehalose give the dynamics at infinite viscosity and are used to separate the viscosity-dependent dynamics from the viscosity-independent dynamics. Although the HbCO dynamics are the same in the red blood cell and in the equivalent aqueous solutions, differences in the absorption spectra show that the distribution of a protein's equilibrium substates is sensitive to small pH differences.     

Effects of Testosterone Replacement on a Male Professional Singer

Testosterone has been known to play an important role in the development of the postpubertal male voice for many centuries. In fact, the prevention of pubertal development of the voice by castrating young male singers was a well-known practice, especially in Italy beginning in the sixteenth century. The “castrati” were well known for their clear, high-pitched voices. Because of the resulting small larynx and vocal folds, castrati apparently produced a distinctive resonance as well as the high pitch, which cannot be matched even by the counter tenors of today. Busy voice labs occasionally see males with sex hormone deficiencies secondary to chromosomal or gonadal problems. This is a presentation of an unusual patient who was a trained tenor singer and was found to have hypogonadism on a premarital health examination. Administration of replacement testosterone resulted in significant vocal register and voice quality changes.     

Orientational dynamics in supercooled liquids near T(c) and comparison with ideal mode-coupling theory

Orientational dynamics in supercooled salol and ortho-terphenyl were measured near their critical temperatures, T(c), with optical Kerr effect experiments spanning a very broad range of times. Above T(c), the decays are shown to be in excellent agreement with the master curve predicted by ideal mode-coupling theory when higher order terms are included. Between the critical decay and the von Schweidler power laws, the intermediate time range of the data can be modeled by a power law. This intermediate power law, located at 2相似文献