Comparison of fluorescence and QCM technologies: Example of explosives detection with a π-conjugated thin film

A π-conjugated compound was synthesized as a sensitive material for explosives detection. The detection of vapors of 2,4-dinitrotoluene was demonstrated with quartz crystal microbalance (QCM) and fluorescence transduction methods. The fluorescence intensity monitoring shows a higher sensitivity and selectivity than the monitoring of the QCM frequency. Both methods appear to be synergic when used simultaneously as the sensor helps to discriminate interferent vapors from nitroaromatics.     

Stereochemical effects during [M-H]− dissociations of epimeric 11-OH-17β-estradiols and distant electronic effects of substituents at C(11) position on gas phase acidity

The affinity of estradiol derivatives for the estrogen receptor (ER) depends strongly on nature and stereochemistry of substituents in C₍₁₁₎ position of the 17β-estradiol (I). In this work, the stereochemistry effects of the 11α-OH-17β-estradiol (III_α) and 11β-OH-17β-estradiol (III_β) were investigated using CID experiments and gas-phase acidity (ΔH_acid^∘) determination. The CID experiments showed that the steroids decompose via different pathways involving competitive dissociations with rate constants depending upon the α/β C₍₁₁₎ stereochemistry. It was shown that the fragmentations of both deprotonated [III_α-H]⁻ and [III_β-H]⁻ epimers were initiated by the deprotonation of the most acidic site, i.e. the phenolic hydroxyl at C₍₃₎. This view was confirmed by H/D exchange and double resonance experiments. Furthermore, the ΔH_acid^∘ of both epimers (III_α and III_β), 17β-estradiol (I), and 17-desoxyestradiol (II) was determined using the extended Cooks’ kinetic method. The resulting values allowed us to classify steroids as a function of their gas-phase acidity as follows: (III_β)≫(II)>(I)>(III_α). Interestingly, the α/β C₍₁₁₎ stereochemistry appeared to influence strongly the gas-phase acidity. This phenomenon could be explained through stereospecific proton interaction with π-orbital cloud of A ring, which was confirmed by theoretical calculation.     

Singly Hydrogen Bonded Supramolecular Ligands for Highly Selective Rhodium‐Catalyzed Hydrogenation Reactions

H bonds make the catalysts! A single hydrogen bond between ligands coordinated to a rhodium center is critical for the formation of pure supramolecular catalysts for asymmetric hydrogenation reactions. The ester group of the amidite ligand (see scheme) also forms a hydrogen bond with the coordinated substrate. Use of the heterocomplex afforded the highest enantioselectivity reported to date for the hydrogenation of several ester substrates.

     

Assessing indoor air exposures using passive sampling with bioanalytical methods for estrogenicity and aryl hydrocarbon receptor activity

Passive air sampling was undertaken using polyurethane foam passive air samplers at three types of locations, including indoors (six offices) at buildings in the central business district (CBD) and at a private suburban home (indoor and outdoor) located 9 km from the CBD in Brisbane, Queensland, Australia. Estrogenic (E-SCREEN—MCF7-BOS) and aryl hydrocarbon receptor (AhR) (CAFLUX—H4G1.1c2) activity were assessed for samples collected from each of these locations. The samples were tested either as crude extracts (“untreated”) or were subjected to H₂SO₄ silica gel (“treated”) for each location in order to determine whether chemicals, which are not resistant to this treatment like polycyclic aromatic hydrocarbons, potentially account for the observed activity. In most cases, H₂SO₄ treatment resulted in a statistically significant reduction of potency for both endpoints, suggesting that chemicals less resistant to treatment may be responsible for much of the detected biological activity in these locations. Estrogenic potency measurements (<0.22–185 pg m⁻³) were highest in the indoor offices, followed by the indoor suburban home and finally the outdoor suburban home (which was not estrogenic). Total AhR activity for crude extracts (1.3–10 pg m⁻³) however was highest for the outdoor suburban home site. Levels of polycyclic aromatic hydrocarbons were monitored indoors and outdoors at the suburban home. At that location, polycyclic aromatic hydrocarbon air concentrations were on average approximately two times higher outdoor than indoor, while AhR potency was five times higher outdoor than indoor. No significant correlation was found between the estrogenic and AhR activity (P = 0.88) for the sites in this study. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The fraction of large random trees representing a given Boolean function in implicational logic

We consider the logical system of Boolean expressions built on the single connector of implication and on positive literals. Assuming all expressions of a given size to be equally likely, we prove that we can define a probability distribution on the set of Boolean functions expressible in this system. Then we show how to approximate the probability of a function f when the number of variables grows to infinity, and that this asymptotic probability has a simple expression in terms of the complexity of f. We also prove that most expressions computing any given function in this system are “simple”, in a sense that we make precise. The probability of all read‐once functions of a given complexity is also evaluated in this model. At last, using the same techniques, the relation between the probability of a function and its complexity is also obtained when random expressions are drawn according to a critical branching process. © 2011 Wiley Periodicals, Inc. Random Struct. Alg., 2011     

Single etch grating couplers for mass fabrication with DUV lithography

Surface grating couplers enable efficient coupling of light between optical fibers and planar waveguide circuits. While traditional grating designs require two etch steps for efficient coupling to silicon-on-insulator waveguides, recently proposed subwavelength structured gratings can achieve the same coupling efficiencies with a single etch step, thereby significantly reducing fabrication complexity. Here we demonstrate that such couplers can be fabricated on a large scale with ultra-violet lithography, achieving a 5?dB coupling efficiency at 1,550?nm. Through both simulations and experiments we give physical insight on how pattern fidelity impacts the performance of these couplers, and propose strategies to deal with inevitable process variations.     

Optimal intermittence in search strategies under speed-selective target detection

Random search theory has been previously explored for both continuous and intermittent scanning modes with full target detection capacity. Here we present a new class of random search problems in which a single searcher performs flights of random velocities, the detection probability when it passes over a target location being conditioned to the searcher speed. As a result, target detection involves an N-passage process for which the mean search time is here analytically obtained through a renewal approximation. We apply the idea of speed-selective detection to random animal foraging since a fast movement is known to significantly degrade perception abilities in many animals. We show that speed-selective detection naturally introduces an optimal level of behavioral intermittence in order to solve the compromise between fast relocations and target detection capability.     

Stability and Instability of the KDV Solitary Wave Under the KP-I Flow

We consider the KP-I and gKP-I equations in \mathbbR × (\mathbbR/2p\mathbbZ){{\mathbb{R}}\,\times\,({\mathbb{R}}/2\pi{\mathbb{Z}})}. We prove that the KdV soliton with subcritical speed 0 < c < c* is orbitally stable under the global KP-I flow constructed by Ionescu and Kenig (Ann Math Stud 163:181–211, 2007). For supercritical speeds c > c*, in the spirit of the work by Duyckaerts and Merle (GAFA 18:1787–1840, 2009), we sharpen our previous instability result and construct a global solution which is different from the solitary wave and its translates and which converges to the solitary wave as time goes to infinity. This last result also holds for the gKP-I equation.     

Minimal non-neighborhood-perfect graphs

Neighborhood-perfect graphs form a subclass of the perfect graphs if the Strong Perfect Graph Conjecture of C. Berge is true. However, they are still not shown to be perfect. Here we propose the characterization of neighborhood-perfect graphs by studying minimal non-neighborhood-perfect graphs (MNNPG). After presenting some properties of MNNPGs, we show that the only MNNPGs with neighborhood independence number one are the 3-sun and 3K₂. Also two further classes of neighborhood-perfect graphs are presented: line-graphs of bipartite graphs and a 3K₂-free cographs. © 1996 John Wiley & Sons, Inc.     

Morphological study of aging phenomena in XLPE by TEM technique

The long-term dielectric performance of underground power cable XLPE (cross-linked polyethylene) insulation suffers from poorly understood aging phenomena. A study of the morphological modifications of XLPE due to electrical aging may provide insight for a better understanding of aging mechanisms. The TEM technique has been used to study the XLPE morphology of unaged, laboratory-aged, and field-aged cable samples. A suitable image contrast enhancing and a stabilization of radiation damage were both successfully achieved by staining the sections with ruthenium tetroxide (RuO₄), as individual XLPE lamellae were neatly and reproducibly resolved. Image analysis was used to help in the determination of any aging-induced morphological changes. XLPE samples from an unaged cable (D1) has been exposed to a low-energy electron beam, in an attempt to simulate certain conditions thought to occur in electric field-stressed dielectrics. © 1996 John Wiley & Sons, Inc.