Simultaneous quantitative profiling of 20 isoprostanoids from omega-3 and omega-6 polyunsaturated fatty acids by LC–MS/MS in various biological samples

Isoprostanoids are a group of non-enzymatic oxygenated metabolites of polyunsaturated fatty acids. It belongs to oxylipins group, which are important lipid mediators in biological processes, such as tissue repair, blood clotting, blood vessel permeability, inflammation and immunity regulation. Recently, isoprostanoids from eicosapentaenoic, docosahexaenoic, adrenic and α-linolenic namely F₃-isoprostanes, F₄-neuroprostanes, F₂-dihomo-isoprostanes and F₁-phytoprostanes, respectively have attracted attention because of their putative contribution to health. Since isoprostanoids are derived from different substrate of PUFAs and can have similar or opposing biological consequences, a total isoprostanoids profile is essential to understand the overall effect in the testing model. However, the concentration of most isoprostanoids range from picogram to nanogram, therefore a sensitive method to quantify 20 isoprostanoids simultaneously was formulated and measured by liquid chromatography-tandem mass spectrometry (LC–MS/MS). The lipid portion from various biological samples was extracted prior to LC–MS/MS evaluation. For all the isoprostanoids LOD and LOQ, and the method was validated on plasma samples for matrix effect, yield of extraction and reproducibility were determined. The methodology was further tested for the isoprostanoids profiles in brain and liver of LDLR^−/− mice with and without docosahexaenoic acid (DHA) supplementation. Our analysis showed similar levels of total F₂-isoprostanes and F₄-neuroprostanes in the liver and brain of non-supplemented LDLR^−/− mice. The distribution of different F₂-isoprostane isomers varied between tissues but not for F₄-neuroprostanes which were predominated by the 4(RS)-4-F_4t-neuroprostane isomer. DHA supplementation to LDLR^−/− mice concomitantly increased total F₄-neuroprostanes levels compared to F₂-isoprostanes but this effect was more pronounced in the liver than brain.     

Conformational dependence of hemoglobin reactivity under high viscosity conditions: the role of solvent slaved dynamics

The concept of protein dynamic states is introduced. This concept is based on (i) protein dynamics being organized hierarchically with respect to solvent slaving and (ii) which tier of dynamics is operative over the time window of a given measurement. The protein dynamic state concept is used to analyze the kinetic phases derived from the recombination of carbon monoxide to sol-gel-encapsulated human adult hemoglobin (HbA) and select recombinant mutants. The temperature-dependent measurements are made under very high viscosity conditions obtained by bathing the samples in an excess of glycerol. The results are consistent with a given tier of solvent slaved dynamics becoming operative at a time delay (with respect to the onset of the measurement) that is primarily solvent- and temperature-dependent. However, the functional consequences of the dynamics are protein- and conformation-specific. The kinetic traces from both equilibrium populations and trapped allosteric intermediates show a consistent progression that exposes the role of both conformation and hydration in the control of reactivity. Iron-zinc symmetric hybrid forms of HbA are used to show the dramatic difference between the kinetic patterns for T state alpha and beta subunits. The overall results support a model for allostery in HbA in which the ligand-binding-induced transition from the deoxy T state to the high -affinity R state proceeds through a progression of T state intermediates.     

Glucose and fructose hydrates in aqueous solution by IR spectroscopy

In the mid-infrared attenuated total reflectance (MIR-ATR) spectra of aqueous d-glucose and d-fructose solutions, two hydrates were found by factor analysis (FA) for each sugar, d-glucose penta- and dihydrates and d-fructose penta- and monohydrates. We obtained the spectra and abundances for these hydrates as a function of carbohydrate concentrations. The biggest difference in these spectra lies in the CO stretch region. From the distribution of the species, the equilibrium between d-glucose pentahydrate and dihydrate is 3(H2O)2+2(C6H12O(6).2H2O) right arrow over left arrow 2(C6H12O(6).5H2O), with the equilibrium constant KG=(3.2+/-0.6)x10(-5) L3 mol-3. For d-fructose, the equilibrium is between pentahydrate and monohydrate, 2(H2O)2+C6H12O6.H2O right arrow over left arrow C6H12O(6).5H2O, with the equilibrium constant KF=(7.1+/-1.2)x10(-3) L2 mol-2. The four hydrates are present only in aqueous solutions and cannot be obtained in the solid state.     

Dynamics of Ultracold Bosons in Artificial Gauge Fields—Angular Momentum,Fragmentation, and the Variance of Entropy

We consider the dynamics of two-dimensional interacting ultracold bosons triggered by suddenly switching on an artificial gauge field. The system is initialized in the ground state of a harmonic trapping potential. As a function of the strength of the applied artificial gauge field, we analyze the emergent dynamics by monitoring the angular momentum, the fragmentation as well as the entropy and variance of the entropy of absorption or single-shot images. We solve the underlying time-dependent many-boson Schrödinger equation using the multiconfigurational time-dependent Hartree method for indistinguishable particles (MCTDH-X). We find that the artificial gauge field implants angular momentum in the system. Fragmentation—multiple macroscopic eigenvalues of the reduced one-body density matrix—emerges in sync with the dynamics of angular momentum: the bosons in the many-body state develop non-trivial correlations. Fragmentation and angular momentum are experimentally difficult to assess; here, we demonstrate that they can be probed by statistically analyzing the variance of the image entropy of single-shot images that are the standard projective measurement of the state of ultracold atomic systems.     

The boundary of the outer space of a free product

Let G be a countable group that splits as a free product of groups of the form G = G ₁ *···* G _k * F _N , where F _N is a finitely generated free group. We identify the closure of the outer space PO(G, {G ₁,..., G _k }) for the axes topology with the space of projective minimal, very small (G, {G ₁,..., G _k })-trees, i.e. trees whose arc stabilizers are either trivial, or cyclic, closed under taking roots, and not conjugate into any of the G _i ’s, and whose tripod stabilizers are trivial. Its topological dimension is equal to 3N + 2k ? 4, and the boundary has dimension 3N + 2k ? 5. We also prove that any very small (G, {G ₁,..., G _k })-tree has at most 2N + 2k?2 orbits of branch points.     

Selection and analytical applications of aptamers binding microbial pathogens

DNA aptamers specifically recognizing microbial cells and viruses have a range of analytical and therapeutic applications. This article describes recent advances in the development of aptamers targeting specific pathogens (e.g., live bacteria, whole viral particles, and virally-infected mammalian cells). Specific aptamers against pathogens have been used as affinity reagents to develop sandwich assays, to label and to image cells, to bind with cells for flow-cytometry analysis, and to act as probes for development of whole-cell biosensors. Future applications of aptamers to pathogens will benefit from recent advances in improved selection and new aptamers containing modified nucleotides, particularly slow off-rate modified aptamers (SOMAmers).     

Spatial resolution optimization of backscattered electron images using Monte Carlo simulation

The relation between probe size and spatial resolution of backscattered electron (BSE) images was studied. In addition, the effect of the accelerating voltage, the current intensity and the sample geometry and composition were analyzed. An image synthesis method was developed to generate the images from backscattered electron coefficients obtained from Monte Carlo simulations. Spatial resolutions of simulated images were determined with the SMART-J method, which is based on the Fourier transform of the image. The resolution can be improved by either increasing the signal or decreasing the noise of the backscattered electron image. The analyses demonstrate that using a probe size smaller than the size of the observed object (sample features) does not improve the spatial resolution. For a probe size larger than the feature size, the spatial resolution is proportional to the probe size.     

Combining coordination chemistry and catalysis to tie a knot by an active-metal template strategy

Collar and tie men: the smallest trefoil knot reported to date has been prepared by an active metal template synthesis. Copper(I) ions are able to constrain the well-designed structure so that it can form the loops by complexing to the bipyridine moieties in the core of the thread and the two ends of the entangled lace on opposite faces of the loop, before acting as a catalyst to close the lace.     

A μ9-iodide in a tricapped trigonal-prismatic geometry

Two luminescent, undecanuclear silver complexes [Ag(11)(μ(9)-I)(μ(3)-I)(3){E(2)P(O(i)Pr)(2)}(6)](PF(6)) [E = S (yellow), 1; Se (orange), 2], containing the first μ(9)-iodine inscribed at the center of a pentacapped trigonal-prismatic silver skeleton, were reported.     

Control and Stabilization of the Korteweg-de Vries Equation on a Periodic Domain

In [38 Russell , D.L. , Zhang , B.-Y. ( 1996 ). Exact controllability and stabilizability of the Korteweg-de Vries equation . Trans. Amer. Math. Soc. 348 : 3643 – 3672 . [Google Scholar]], Russell and Zhang showed that the Korteweg-de Vries equation posed on a periodic domain  with an internal control is locally exactly controllable and locally exponentially stabilizable when the control acts on an arbitrary nonempty subdomain of . In this paper, we show that the system is in fact globally exactly controllable and globally exponentially stabilizable. The global exponential stabilizability is established with the aid of certain properties of propagation of compactness and regularity in Bourgain spaces for the solutions of the associated linear system. With Slemrod's feedback law, the resulting closed-loop system is shown to be locally exponentially stable with an arbitrarily large decay rate. A time-varying feedback law is further designed to ensure a global exponential stability with an arbitrarily large decay rate.