Nonequilibrium fluctuation induced escape from a metastable state

Based on a simple microscopic model where the bath is in a non-equilibrium state we study the escape from a metastable state in the over-damped limit. Making use of Fokker-Planck-Smoluchowski description we derive the time dependent escape rate in the non-stationary regime in closed analytical form which brings on to fore a strong non-exponential kinetic of the system mode.Comment: 4 pages, no figures, EPJ class file include

Impact of ivermectin administered for scabies treatment on the prevalence of head lice in Atoifi, Solomon Islands.

Scabies and head lice are ubiquitous ectoparasitic infestations that are common across the Pacific Islands. Ivermectin is an effective treatment for both conditions, although the doses used vary. At a community level, mass drug administration (MDA) with ivermectin is an effective strategy to decrease prevalence of scabies. To what extent MDA with ivermectin will also reduce prevalence of head lice is unknown. Head lice prevalence was assessed before and after MDA with oral ivermectin (at a dose of 200 micrograms per kilogram of body weight) administered on day 1 and day 8. The primary outcome was the change in prevalence of head louse infestation at two weeks compared to baseline. Longer term efficacy was assessed three months after MDA. 118 participants were enrolled. Baseline prevalence of active head louse infestation was 25.4% (95% CI 18.4-34.0). At three-month follow-up, prevalence was 7.5% (95% CI 2.7-12.3), a relative reduction of 70.6% (95% CI 72.7%-91.4%, p <0.001). Head louse infestation was associated with younger age (age ≤10 years: prevalence 46.7%; adjusted odds ratio compared to adults of 7.2, 95%CI 2.0-25.9) and with having at least one other member of the household with active head louse infestation (adjusted odds ratio 4.3, 95%CI 1.7-11.1). Head louse infestation is common in the Solomon Islands. This proof of principle study shows that oral ivermectin at a dose of 200 micrograms per kilogram can reduce the burden of active head louse infestation, offering an additional collateral benefit of MDA with ivermectin for scabies control. ClinicalTrials.gov NCT03236168

Time-dependent photoionization of azulene: Optically induced anisotropy on the femtosecond scale

We measure the photoionization cross-section of vibrationally excited levels in the S2 state of azulene by femtosecond pump-probe spectroscopy. At the wavelengths studied (349-265 nm in the pump) the transient signals exhibit two distinct and well-defined behaviours: (i) Short-term (on the order of a picosecond) polarization dependent transients and (ii) longer (10 ps - 1 ns) time-scale decays. This letter focuses on the short time transient. In contrast to an earlier study by Diau et al.22 [J. Chem. Phys. 110 (1999) 9785.] we unambiguously assign the fast initial decay signal to rotational dephasing of the initial alignment created by the pump transition.Comment: Chemical Physics Letters (2008

Hole dynamics in noble metals

We present a detailed analysis of hole dynamics in noble metals (Cu and Au), by means of first-principles many-body calculations. While holes in a free-electron gas are known to live shorter than electrons with the same excitation energy, our results indicate that d-holes in noble metals exhibit longer inelastic lifetimes than excited sp-electrons, in agreement with experiment. The density of states available for d-hole decay is larger than that for the decay of excited electrons; however, the small overlap between d- and sp-states below the Fermi level increases the d-hole lifetime. The impact of d-hole dynamics on electron-hole correlation effects, which are of relevance in the analysis of time-resolved two-photon photoemission experiments, is also addressed.Comment: 4 pages, 2 figures, to appear in Phys. Rev. Let

Design and characterization of alkoxy-wrapped push-pull porphyrins for dye-sensitized solar cells

Three alkoxy-wrapped push-pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular design

The influence of long chain polyunsaturate supplementation on docosahexaenoic acid and arachidonic acid in baboon neonate central nervous system

BACKGROUND: Docosahexaenoic acid (DHA) and arachidonic acid (ARA) are major components of the cerebral cortex and visual system, where they play a critical role in neural development. We quantitatively mapped fatty acids in 26 regions of the four-week-old breastfed baboon CNS, and studied the influence of dietary DHA and ARA supplementation and prematurity on CNS DHA and ARA concentrations. METHODS: Baboons were randomized into a breastfed (B) and four formula-fed groups: term, no DHA/ARA (T-); term, DHA/ARA supplemented (T+); preterm, no DHA/ARA (P-); preterm and DHA/ARA supplemented (P+). At four weeks adjusted age, brains were dissected and total fatty acids analyzed by gas chromatography and mass spectrometry. RESULTS: DHA and ARA are rich in many more structures than previously reported. They are most concentrated in structures local to the brain stem and diencephalon, particularly the basal ganglia, limbic regions, thalamus and midbrain, and comparatively lower in white matter. Dietary supplementation increased DHA in all structures but had little influence on ARA concentrations. Supplementation restored DHA concentrations to levels of breastfed neonates in all regions except the cerebral cortex and cerebellum. Prematurity per se did not exert a strong influence on DHA or ARA concentrations. CONCLUSION: 1) DHA and ARA are found in high concentration throughout the primate CNS, particularly in gray matter such as basal ganglia; 2) DHA concentrations drop across most CNS structures in neonates consuming formulas with no DHA, but ARA levels are relatively immune to ARA in the diet; 3) supplementation of infant formula is effective at restoring DHA concentration in structures other than the cerebral cortex. These results will be useful as a guide to future investigations of CNS function in the absence of dietary DHA and ARA

FADS2 Function Loss at the Cancer Hotspot 11q13 Locus Diverts Lipid Signaling Precursor Synthesis to Unusual Eicosanoid Fatty Acids

Background: Genes coding for the fatty acid desaturases (FADS1, 2, 3) localized at the cancer genomic hotspot 11q13 locus are required for the biosynthesis of 20 carbon polyunsaturated fatty acids (PUFA) that are direct eicosanoid precursors. In several cancer cell lines, FADS2 encoded D6 and D8 desaturation is not functional. Methodology/Principal Findings: Analyzing MCF7 cell fatty acids with detailed structural mass spectrometry, we show that in the absence of FADS2 activity, the FADS1 product D5-desaturase operates to produce 5,11,14–20:3 and 5,11,14,17–20:4. These PUFA are missing the 8–9 double bond of the eicosanoid signaling precursors arachidonic acid (5,8,11,14–20:4) and eicosapentaenoic acid (5,8,11,14,17–20:5). Heterologous expression of FADS2 restores D6 and D8-desaturase activity and normal eicosanoid precursor synthesis. Conclusions/Significance: The loss of FADS2-encoded activities in cancer cells shuts down normal PUFA biosynthesis, deleting the endogenous supply of eicosanoid and downstream docosanoid precursors, and replacing them with unusual butylene-interrupted fatty acids. If recapitulated in vivo, the normal eicosanoid and docosanoid cell signaling milieu would be depleted and altered due to reduction and substitution of normal substrates with unusual substrates, with unpredictable consequences for cellular communication

Differential Cerebral Cortex Transcriptomes of Baboon Neonates Consuming Moderate and High Docosahexaenoic Acid Formulas

BACKGROUND: Docosahexaenoic acid (DHA, 22:6n-3) and arachidonic acid (ARA, 20:4n-6) are the major long chain polyunsaturated fatty acids (LCPUFA) of the central nervous system (CNS). These nutrients are present in most infant formulas at modest levels, intended to support visual and neural development. There are no investigations in primates of the biological consequences of dietary DHA at levels above those present in formulas but within normal breastmilk levels. METHODS AND FINDINGS: Twelve baboons were divided into three formula groups: Control, with no DHA-ARA; “L”, LCPUFA, with 0.33%DHA-0.67%ARA; “L3”, LCPUFA, with 1.00%DHA-0.67%ARA. All the samples are from the precentral gyrus of cerebral cortex brain regions. At 12 weeks of age, changes in gene expression were detected in 1,108 of 54,000 probe sets (2.05%), with most showing <2-fold change. Gene ontology analysis assigns them to diverse biological functions, notably lipid metabolism and transport, G-protein and signal transduction, development, visual perception, cytoskeleton, peptidases, stress response, transcription regulation, and 400 transcripts having no defined function. PLA2G6, a phospholipase recently associated with infantile neuroaxonal dystrophy, was downregulated in both LCPUFA groups. ELOVL5, a PUFA elongase, was the only LCPUFA biosynthetic enzyme that was differentially expressed. Mitochondrial fatty acid carrier, CPT2, was among several genes associated with mitochondrial fatty acid oxidation to be downregulated by high DHA, while the mitochondrial proton carrier, UCP2, was upregulated. TIMM8A, also known as deafness/dystonia peptide 1, was among several differentially expressed neural development genes. LUM and TIMP3, associated with corneal structure and age-related macular degeneration, respectively, were among visual perception genes influenced by LCPUFA. TIA1, a silencer of COX2 gene translation, is upregulated by high DHA. Ingenuity pathway analysis identified a highly significant nervous system network, with epidermal growth factor receptor (EGFR) as the outstanding interaction partner. CONCLUSIONS: These data indicate that LCPUFA concentrations within the normal range of human breastmilk induce global changes in gene expression across a wide array of processes, in addition to changes in visual and neural function normally associated with formula LCPUFA

Mechanistic Insights into Ring-Opening and Decarboxylation of 2-Pyrones in Liquid Water and Tetrahydrofuran

2-Pyrones, such as triacetic acid lactone, are a promising class of biorenewable platform chemicals that provide access to an array of chemical products and intermediates. We illustrate through the combination of results from experimental studies and first-principle density functional theory calculations that key structural features dictate the mechanisms underlying ring-opening and decarboxylation of 2-pyrones, including the degree of ring saturation, the presence of C═C bonds at the C4═C5 or C5═C6 positions within the ring, as well as the presence of a β-keto group at the C4 position. Our results demonstrate that 2-pyrones undergo a range of reactions unique to their structure, such as retro-Diels–Alder reactions and nucleophilic addition of water. In addition, the reactivity of 2-pyrones and the final products formed is shown to depend on the solvent used and the acidity of the reaction environment. The mechanistic insights obtained here provide guidance for the selective conversion of 2-pyrones to targeted chemicals.Reprinted (adapted) with permission from Journal of American Chemical Society, 135(15); 5699-5708. Doi: 10.1021/ja312075r. Copyright 2013 American Chemical Society. </p