Cytochrome c552 mutants: structure and dynamics at the active site probed by multidimensional NMR and vibration echo spectroscopy

Spectrally resolved infrared stimulated vibrational echo experiments are used to measure the vibrational dephasing of a CO ligand bound to the heme cofactor in two mutated forms of the cytochrome c552 from Hydrogenobacter thermophilus. The first mutant (Ht-M61A) is characterized by a single mutation of Met61 to an Ala (Ht-M61A), while the second variant is doubly modified to have Gln64 replaced by an Asn in addition to the M61A mutation (Ht-M61A/Q64N). Multidimensional NMR experiments determined that the geometry of residue 64 in the two mutants is consistent with a non-hydrogen-bonding and hydrogen-bonding interaction with the CO ligand for Ht-M61A and Ht-M61A/Q64N, respectively. The vibrational echo experiments reveal that the shortest time scale vibrational dephasing of the CO is faster in the Ht-M61A/Q64N mutant than that in Ht-M61A. Longer time scale dynamics, measured as spectral diffusion, are unchanged by the Q64N modification. Frequency-frequency correlation functions (FFCFs) of the CO are extracted from the vibrational echo data to confirm that the dynamical difference induced by the Q64N mutation is primarily an increase in the fast (hundreds of femtoseconds) frequency fluctuations, while the slower (tens of picoseconds) dynamics are nearly unaffected. We conclude that the faster dynamics in Ht-M61A/Q64N are due to the location of Asn64, which is a hydrogen bond donor, above the heme-bound CO. A similar difference in CO ligand dynamics has been observed in the comparison of the CO derivative of myoglobin (MbCO) and its H64V variant, which is caused by the difference in axial residue interactions with the CO ligand. The results suggest a general trend for rapid ligand vibrational dynamics in the presence of a hydrogen bond donor.     

A tandem synthesis of 3-aroylcoumarinoflavones catalyzed by <Emphasis Type="SmallCaps">l</Emphasis>-proline and their antioxidant activity

A facile, convenient, efficient and high-yielding synthesis of 3-aroylcoumarinoflavones has been developed by the condensation of easily synthesized 7-hydroxy-8-formylflavones and benzoyl acetonitriles in the presence of catalytic amount of l-proline in ethanol reflux. All the synthesized compounds were evaluated for their antioxidant activity. Some of the compounds showed very good activity compared to standard BHT.     

Coefficient estimates of negative powers and inverse coefficients for certain starlike functions

For ?1≤B<A≤1, let \(\mathcal {S}^{*}(A,B)\) denote the class of normalized analytic functions \(f(z)= z+{\sum }_{n=2}^{\infty }a_{n} z^{n}\) in |z|<1 which satisfy the subordination relation z f ^′(z)/f(z)?(1 + A z)/(1 + B z) and Σ^?(A,B) be the corresponding class of meromorphic functions in |z|>1. For \(f\in \mathcal {S}^{*}(A,B)\) and λ>0, we shall estimate the absolute value of the Taylor coefficients a _n (?λ,f) of the analytic function (f(z)/z)^?λ . Using this we shall determine the coefficient estimate for inverses of functions in the classes \(\mathcal {S}^{*}(A,B)\) and Σ^?(A,B).     

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (T_NTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of T_NTBN was estimated for CBO3OCB and T_NTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of T_NTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.     

Water dynamics in small reverse micelles in two solvents: two-dimensional infrared vibrational echoes with two-dimensional background subtraction

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w(0) = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w(0) = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w(0), but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl(4) system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.     

The Prevalence of Helicobacter Pylori Infection in Benign Laryngeal Disorders

Helicobacter pylori (HP) is an accepted cause of chronic active gastritis and has a major causative role in peptic ulcers. It is a gastric carcinogen. Its role in nonulcer dyspepsia (NUD) is less clear, yet 50% of patients with NUD are infected with HP, and some recent literature demonstrates long-term improvement of symptoms following eradication. HP has been investigated in several other organ systems, but has not been investigated to any major degree in laryngeal disorders, a region that could be directly exposed to the bacterium from pharyngolaryngeal reflux. This study represents one arm of a larger study designed to investigate such a relationship. Of 101 patients with nonmalignant voice disorders presenting to our voice clinics, 54.5% tested positive for the H. pylori organism. Of the controls, 47.1% tested positive. When striated into age groups of < 45 years, 46–61 years, and > 62 years, and then age-matched with the controls, the likelihood of infection with the H. pylori organism was greater in both the experimental middle group, and in the middle group when combined with the elder group, than in the matched controls, and this difference demonstrated a trend approaching statistical significance. This finding is discussed in the light of other studies on HP and on gastroesophageal reflex (GER).     

Study of ΛΛ dynamics and ground state structure of low and medium mass double Λ hypernuclei

We critically review the ΛΛ dynamics by examining Λ - Λ and Λ-nucleon phenomenological potentials in the study of the bound state properties of double-Λ hypernuclei _ΛΛ ⁶ He, _ΛΛ ¹⁰ Be, _ΛΛ ¹⁴ C, _ΛΛ ¹⁸ O, _ΛΛ ²² Ne, _ΛΛ ²⁶ Mg, _ΛΛ ³⁰ Si, _ΛΛ ³⁴ S, _ΛΛ ³⁸ Ar, _ΛΛ ⁴² Ca, _ΛΛ ⁴⁶ Ti, _ΛΛ ⁵⁰ Cr, _ΛΛ ⁵⁴ Fe, _ΛΛ ⁵⁸ Ni, _ΛΛ ⁶² Zn, _ΛΛ ⁶⁶ Ge, _ΛΛ ⁷⁰ Se, _ΛΛ ⁷⁴ Kr, _ΛΛ ⁷⁸ Sr, _ΛΛ ⁸² Zr, _ΛΛ ⁸⁶ Mo, _ΛΛ ⁹⁰ Ru, _ΛΛ ⁹⁴ Pd, _ΛΛ ⁹⁸ Cd, _ΛΛ ¹⁰² Sn in the frame work of (core+Λ+Λ) three body model. An effective ΛN potential is obtained by folding the phenomenological ΛN potential into the density distribution of the core nuclei. The former two cases (i.e. _ΛΛ ⁶ He and _ΛΛ ¹⁰ Be) are revisited to justify the correctness of the present potential model. Assuming the same potential model we predicted some of the structural properties of heavier doubly Λ-hypernuclei. The hyperspherical harmonics expansion method, which is an essentially exact method has been employed for the three body system. A convergence in binding energy up to 0.15% for K _max=20 has been achieved. In our calculation we have made no approximation in restricting the allowed l-values of the interacting pairs.     

The Inspiratory Maneuver: A Simple Method to Assess the Superficial Lamina Propria During Endoscopy

We describe a simple means of assessing the condition of the superficial lamina propria during endoscopy, which we use in our practice as an adjunct to careful stroboscopic examination. An intake of breath against partially adducted vocal folds serves to draw the mucosa inferomedially into the glottis, which reveals areas of diminished mobility, the relationship of mucosal lesions to deeper tissues of the vocal folds, and subtle submucosal lesions. This is possible because of the unique geometry of the glottis that renders the vector forces of airflow different at inspiration and expiration. Because the integrity of the superficial lamina propria is essential to healthy phonation, we have found the inspiratory maneuver useful across a wide variety of mucosal pathologic conditions.     

Experiment and prediction of a cavity type separated flow

A detail study involving flow visualization, Laser Doppler Velocimeter (LDV) measurements and numerical prediction is presented. The visualization experiments revealed striking results of a pulsatile motion in the separated flow region associated with the formation and passage of large eddy structures. Measurements of mean velocities and turbulence intensity profiles across the separated flow field, provided information about the separated shear layer development and the recirculating flow pattern. The numerical predictions, obtained with a two-layer turbulence model in conjunction with the SIMPLE algorithm, failed to reproduce the coherent eddies and the pulsatile motion, but the mean velocities are reasonably reproduced.