Microscopic quantum coherence in a photosynthetic-light-harvesting antenna

We briefly review the coherent quantum beats observed in recent two-dimensional electronic spectroscopy experiments in a photosynthetic-light-harvesting antenna. We emphasize that the decay of the quantum beats in these experiments is limited by ensemble averaging. The in vivo dynamics of energy transport depends upon the local fluctuations of a single photosynthetic complex during the energy transfer time (a few picoseconds). Recent analyses suggest that it remains possible that the quantum-coherent motion may be robust under individual realizations of the environment-induced fluctuations contrary to intuition obtained from condensed phase spectroscopic measurements and reduced density matrices. This result indicates that the decay of the observed quantum coherence can be understood as ensemble dephasing. We propose a fluorescence-detected single-molecule experiment with phase-locked excitation pulses to investigate the coherent dynamics at the level of a single molecule without hindrance by ensemble averaging. We discuss the advantages and limitations of this method. We report our initial results on bulk fluorescence-detected coherent spectroscopy of the Fenna-Mathews-Olson complex.     

Azido and Diazarinyl Analogues of Bis‐Tyrphostin as Asymmetrical Inhibitors of Dynamin GTPase

Probing the dynamin binding site : Bis‐tyrphostin ( 1 , Bis‐T), is a potent inhibitor of the phospholipid‐stimulated GTPase activity of dynamin I. Analogues of Bis‐T have significant potential as a biological probes for the dissection of endocytic pathways. Bis‐T‐derived compounds were synthesised and evaluated for their ability to inhibit the GTPase activity of dynamin I. Two analogues ( 23 and 24 ) represent the first asymmetrically substituted Bis‐T analogues to retain dynamin inhibition.

     

Inhibition of hydrogen oxidation by HBr and Br2

The high-temperature bromine chemistry was updated and the inhibition mechanisms involving HBr and Br₂ were re-examined. The thermochemistry of the bromine species was obtained using the Active Thermochemical Tables (ATcT) approach, resulting in improved data for, among others, Br, HBr, HOBr and BrO. Ab initio calculations were used to obtain rate coefficients for selected reactions of HBr and HOBr, and the hydrogen/bromine/oxygen reaction mechanism was updated. The resulting model was validated against selected experimental data from the literature and used to analyze the effect of HBr and Br₂ on laminar, premixed hydrogen flames. Our work shows that hydrogen bromide and molecular bromine act differently as inhibitors in flames. For HBr, the reaction HBr + H ? H₂ + Br (R2) is rapidly equilibrated, depleting HBr in favor of atomic Br, which is the major bromine species throughout the reaction zone. The chain-breaking steps are then H + Br + M → HBr + M (R1), Br + HO₂ → HBr + O₂ (R7), and Br + Br + M → Br₂ + M (R8). In Br₂-doped flames, the reaction Br₂ + H ? HBr + Br (R9) is far from equilibration and serves to deplete H in the reaction zone by competing with H + O₂ → O + OH. The inhibition is augmented by recombination of Br (R8). If the inlet Br₂ mole fraction exceeds about 20%, reactions (R8), (R2) are both reversed, now acting to promote chain branching and increase the flame speed. According to the present model, cycles involving HOBr are not important for generation or removal of chain carriers in these flames.     

Silica coated paper substrate for paper-spray analysis of therapeutic drugs in dried blood spots

Paper spray is a newly developed ambient ionization method that has been applied for direct qualitative and quantitative analysis of biological samples. The properties of the paper substrate and spray solution have a significant impact on the release of chemical compounds from complex sample matrices, the diffusion of the analytes through the substrate, and the formation of ions for mass spectrometry analysis. In this study, a commercially available silica-coated paper was explored in an attempt to improve the analysis of therapeutic drugs in dried blood spots (DBS). The dichloromethane/isopropanol solvent has been identified as an optimal spray solvent for the analysis. The comparison was made with paper spray using chromatography paper as substrate with methanol/water as solvent for the analysis of verapamil, citalopram, amitriptyline, lidocaine, and sunitinib in dried blood spots. It has been demonstrated that the efficiency of recovery of the analytes was notably improved with the silica coated paper and the limit of quantitation (LOQ) for the drug analysis was 0.1 ng mL(-1) using a commercial triple quadrupole mass spectrometer. The use of silica paper substrate also resulted in a sensitivity improvement of 5-50-fold in comparison with chromatography papers, including the Whatman ET31 paper used for blood cards. Analysis using a hand-held miniature mass spectrometer Mini 11 gave LOQs of 10-20 ng mL(-1) for the tested drugs, which is sufficient to cover the therapeutic ranges of these drugs.     

Structure and Dynamic Mechanical Properties of Melt Intercalated Polyamide 6—Montmorillonite Nanocomposites

Summary: Polymer‐layered silicate nanocomposites (PLSN), based on polyamide 6 (PA6) and montmorillonite (MMT) modified with an octadecylammonium salt, were produced via melt compounding in a co‐rotating twin‐screw extruder. Wide angle X‐ray diffraction (WAXD) and TEM revealed a PLSN containing 3.3% by weight (wt.‐%) of MMT to exhibit a mixed exfoliated/intercalated morphology, consisting mainly of individual silicate lamellae together with some intercalated stacks, resulting in a mean value of 1.8 lamellae per particle. In contrast, a PLSN containing a higher level of 7.2 wt.‐% MMT exhibited a more ordered intercalated structure, consisting mainly of a distribution of lamellae stacks with a mean value of 3.8 lamellae per particle. The dispersion of MMT in the PLSN generated very large polymer–filler interfacial areas, resulting in significant increase in the volume of constrained PA6 chain segments. Consequently, significant changes in the ratio of α/γ crystallites and in the thermal behaviour of the matrix PA6 were observed during WAXD, DSC and dynamic‐mechanical thermal analysis (DMTA) studies of the PLSN. In particular, damping data from DMTA showed relaxations between T_g and T_m resulting from amorphous polymer chain segments constrained at the polymer–filler interface, indicating the formation of a continuous phase of constrained polymer. In contrast, a PA6 microcomposite formed using unmodified MMT generated much lower polymer–filler interfacial area, with most of the MMT residing within large, poorly wetted aggregates. Consequently, changes to the thermal behaviour of the matrix PA6 were much less significant than those induced in the PLSN.

Shear storage modulus (G′) versus temperature data for the matrix PA6, the 5T and 10T PLSN and the 5P microcomposite.     

Synthesis and two-photon photolysis of 6-(ortho-nitroveratryl)-caged IP3 in living cells

The synthesis of a photolabile derivative of inositol-1,4,5-trisphosphate (IP3) is described. This new caged second messenger (6-ortho-nitroveratryl)-IP3 (6-NV-IP3) has an extinction coefficient of 5000 M(-1) cm(-1) at 350 nm, and a quantum yield of photolysis of 0.12. Therefore, 6-NV-IP3 is photolyzed with UV light about three times more efficiently than the widely used P(4(5))-1-(2-nitrophenyl)ethyl-caged IP3 (NPE-IP3). 6-NV-IP3 has a two-photon cross-section of about 0.035 GM at 730 nm. This absorbance is sufficiently large for effective two-photon excitation in living cells at modest power levels. Using near-IR light (5 mW, 710 nm, 80 MHz, pulse-width 70 fs), we produced focal bursts of IP3 in HeLa cells, as revealed by laser-scanning confocal imaging of intracellular Ca2+ concentrations. Therefore, 6-NV-IP3 can be used for efficient, subcellular photorelease of IP3, not only in cultured cells but also, potentially, in vivo. It is in the latter situation that two-photon photolysis should reveal its true forte.     

Daily Mood, Partner Support, Sexual Interest, and Sexual Activity Among Adolescent Women.

The main objective of this study was to examine day-to-day associations of coitus, sexual interest, partner emotional support, negative mood, and positive mood among adolescent women. Diaries assessed partner interactions, sexual activity, substance use, and mood. Participants were 146 adolescent women who provided 28,376 diary days. Correlates of coitus on a given day included age, increased coital frequency in previous week, coitus on the previous day, partner support, increased same-day sexual interest, and decreased same-day negative mood. The data demonstrate complex associations of sexual interest, mood, partner interactions, and sexual activity. The findings extend understanding of the sexuality of adolescent women and have implications for a variety of interventions to reduce sexually transmitted infections and unplanned pregnancies. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A randomized trial of cognitive therapy and imaginal exposure in the treatment of chronic posttraumatic stress disorder.

A randomized trial was performed in which imaginal exposure (IE) and cognitive therapy (CT) were compared in the treatment of chronic posttraumatic stress disorder (PTSD). Patients who continued to meet PTSD caseness at the end of a 4-week symptom-monitoring baseline period (n?=?72) were randomly allocated to either IE or CT. There was a significant improvement in all measures over treatment and at follow-up, although there were no significant differences between the 2 treatments at any assessment. A significantly greater number of patients who showed worsening over treatment received IE, although this effect was not found at follow-up. Patients who worsened showed a greater tendency to miss treatment sessions, rated therapy as less credible, and were rated as less motivated by the therapist. It was concluded that either exposure or a challenge to cognition can result in symptom reduction, although neither resulted in complete improvement. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Validating analytical judgments: the case of the airbag''s lifesaving effectiveness

Based primarily on experimental testing and engineering judgment, early evaluations of airbags made variable predictions of their lifesaving benefits. The official estimates of the US government from 1977 to 1987 were that between 6000 and 9000 lives could be saved each year if all passenger cars were equipped with full-front airbags. Now, over a decade later, extensive real-world crash experience in the US has been analyzed to validate early predictions. Lifesaving estimates have been revised downward and the official US government position in 1997 was that, overall, approximately 3000 lives will be saved each year when the vehicle fleet is fully-equipped with frontal airbags. This article explores the reasons for poor validity of early lifesaving forecasts for airbags. We found that airbag effectiveness for unbelted adult occupants was overestimated, the number of adult motorists who would wear safety belts was underestimated, and that early analyses generally did not adequately address heterogeneity in the vehicle fleet or people. For each source of error, we discuss why technical specialists may have erred and what lessons can be gleaned from this case study in validation.