A neutron scattering study of the structure and water partitioning of selectively deuterated copolymer micelles

We present a scattering study of a selectively deuterated micelle-forming diblock copolymer. The copolymer comprises a partially deuterated polystyrene (d,h-PS) block and an imidazolium-functionalized PS (IL) block. In toluene solutions, the copolymers assemble into elongated micelles where the IL block forms the micelle core. Through dynamic light scattering (DLS) measurements, we obtain the overall size of the micelles. In our small-angle neutron scattering (SANS) studies, we use contrast matching to characterize the IL core and the PS shell of the micelles independently. The PS block forming the micelle shell exhibits either a starlike or brushlike conformation depending upon the size of the core to which it is tethered. We find the IL block to be in an extended conformation, driving the formation of slightly elongated and relatively stiff micelle cores. The elongated micelle core cross-sectional radius and length depend linearly on the length of the IL block. We find that the micelles can sequester a few water molecules for each IL repeat unit; the addition of water slightly increases the cross section of the elongated micelles.     

Nickel‐Catalyzed N‐Arylation of Primary Amides and Lactams with Activated (Hetero)aryl Electrophiles

The first nickel‐catalyzed N‐arylation of amides with (hetero)aryl (pseudo)halides is reported, enabled by use of the air‐stable pre‐catalyst (PAd‐DalPhos)Ni(o‐tolyl)Cl ( C1 ). A range of structurally diverse primary amides and lactams were cross‐coupled successfully with activated (hetero)aryl chloride, bromide, triflate, tosylate, mesylate, and sulfamate electrophiles.     

Evidence for C-H...O=C bonding in coadsorbed aromatic-carbonyl systems on Pt(111)

The coadsorption of ethyl formate, acetone, and methyl pyruvate with benzene and naphthalene on Pt(111) was studied with reflection absorption infrared spectroscopy (RAIRS) and thermal desorption (TPD) measurements. Coadsorbed benzene or naphthalene are found to convert eta1- and eta2-states of ethyl formate and acetone into new states displaying slightly red-shifted carbonyl bands. Similarly, coadsorption converts the enediolate state of methyl pyruvate into a new adsorption geometry in which the carbonyl bands are silent. In each case, coadsorption of the aromatic leads to significantly modified carbonyl desorption spectra. The results suggest an attractive carbonyl-aromatic interaction that weakens or removes the direct interaction of the carbonyl function with the metal surface. The aromatic-carbonyl interaction is attributed to hydrogen bonding between C-H and C=O, enhanced by the chemisorption induced polarization of the aromatic.     

Toward Thiophene‐Annulated Graphene Nanoribbons

Narrow thiophene‐edged graphene nanoribbons (GNRs) were prepared from polychlorinated thiophene‐containing poly(p‐phenylene)s using the photochemical, metal‐free cyclodehydrochlorination (CDHC) reaction. ¹H NMR and Raman spectroscopy confirmed the structures of the GNRs. The regioselectivity of the CDHC reaction allows the preparation of both laterally symmetrical and unsymmetrical GNRs and, consequently, the modulation of their optical and electronic properties.     

Characterization of xylazine metabolism in rat liver microsomes using liquid chromatography–hybrid triple quadrupole–linear ion trap–mass spectrometry

ABSTRACT: Xylazine is an α₂‐adrenoceptor agonist and it is widely used in veterinary anesthesia in combination with ketamine. There is limited information on the metabolism of xylazine. A quantitative method for the determination of xylazine by HPLC‐ESI/MS/MS was developed. The method consisted of a protein precipitation extraction followed by analysis using liquid chromatography electrospray tandem mass spectrometry. The chromatographic separation was achieved using a Thermo Betasil Phenyl 100 × 2 mm column combined with an isocratic mobile phase composed of acetonitrile, methanol, water and formic acid (60:20:20:0.4) at a flow rate of 300 μL/min. The mass spectrometer was operating in selected reaction monitoring mode and the analytical range was set at 0.05–50 μm . The precision (%CV) and accuracy (%NOM) observed were 2.3–7.2 and 88.2–96.4%. In vitro metabolism studies were performed in rat liver microsomes and results showed moderate cytochrome P450 affinity (K_m = 10.1 μm ) and a low metabolic stability of xylazine with a half‐life of 4.1 min in rat liver microsomes. Five phase 1 metabolites were observed. The main metabolite observed was an oxidation of the thiazine moiety at m/z 235 and, to a lesser extent, we observed the formation of N‐(2,6‐dimethylphenyl)thiourea at m/z 181 and three distinctive hydroxylated metabolites at m/z 237. Further experiments with ketamine and ketoconazole strongly supported that the metabolism of xylazine to its main metabolite is mediated by CYP3A in rat liver microsomes. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis, Cu(II) complexation, 64Cu-labeling and biological evaluation of cross-bridged cyclam chelators with phosphonate pendant arms

A new class of cross-bridged cyclam-based macrocycles featuring phosphonate pendant groups has been developed. 1,4,8,11-tetraazacyclotetradecane-1,8-di(methanephosphonic acid) (CB-TE2P, 1) and 1,4,8,11-tetraazacyclotetradecane-1-(methanephosphonic acid)-8-(methanecarboxylic acid) (CB-TE1A1P, 2) have been synthesized and have been shown to readily form neutral copper(II) complexes at room temperature as the corresponding dianions. Both complexes showed high kinetic inertness to demetallation and crystal structures confirmed complete encapsulation of copper(II) ion within each macrocycle's cleft-like structure. Unprecedented for cross-bridged cyclam derivatives, both CB-TE2P (1) and CB-TE1A1P (2) can be radiolabeled with (64)Cu at room temperature in less than 1 h with specific activities >1 mCi μg(-1). The in vivo behavior of both (64)Cu-CB-TE2P and (64)Cu-CB-TE1A1P were investigated through biodistribution studies using healthy male Lewis rats. Both new compounds showed rapid clearance with similar or lower accumulation in non-target organs/tissues when compared to other copper chelators including CB-TE2A, NOTA and Diamsar.     

New labdane diterpenes from the stem bark of Larix laricina

Two new labdane diterpenes, cis-19-hydroxyabienol (1) and 8alpha-hydroxy-12Z,14-labdadien-19-al (2), along with another labdane described for the first time in the genus Larix, 19-acetoxy-13S-hydroxy-8(17),14-labdadiene (3) and a stilbene, 3-methoxy-3,3',5'-trihydroxystilbene (4), were isolated from the stem bark of Larch (Larix laricina). Their structures were established by standard chemical and spectroscopic methods. Compounds 2 and 3 were shown to be moderately cytotoxic against A-549, DLD-1 and normal skin fibroblast cell lines, WS1. Compound 1 was found to be selectively active against colon carcinoma cell lines, DLD-1.     

Experimental bound entanglement in a four-photon state

Bound entanglement is central to many exciting theoretical results in quantum information processing, but has thus far not been experimentally realized. In this work, we consider a one-parameter family of four-qubit Smolin states. We experimentally produce these states in the polarization of four optical photons produced from parametric down-conversion. Within a range of the parameter, we show that our states are entangled and undistillable, and thus bound entangled. Using these bound-entangled states we demonstrate entanglement unlocking.     

Finite-Dimensional Bicomplex Hilbert Spaces

This paper is a detailed study of finite-dimensional modules defined on bicomplex numbers. A number of results are proved on bicomplex square matrices, linear operators, orthogonal bases, self-adjoint operators and Hilbert spaces, including the spectral decomposition theorem. Applications to concepts relevant to quantum mechanics, like the evolution operator, are pointed out.     

Experimental estimation of fluctuating velocity and scalar gradients in turbulence

The effect of numerical differentiation is investigated in the context of evaluating fluctuating velocity and scalar quantities in turbulent flows. In particular, 2-point forward-difference and 3-, 5-, 7-, and 9-point centred-difference schemes are investigated. The spectral technique introduced by Wyngaard (in J Sci Instr 1(2):1105–1108, 1968) for homogeneous turbulence is used to quantify the effects of the schemes. Numerical differentiation is shown to attenuate gradient spectra over a range of wavenumbers. The spectral attenuation, which varies with the order of the scheme, results in a reduction in the measured mean-squared gradients. High-order schemes (e.g. 7- or 9-point) are shown to significantly decrease the attenuation at all wavenumbers and as a result produce more accurate gradients. Hot-wire measurements and direct numerical simulations of decaying homogeneous, isotropic turbulence are found to be in good agreement with the predictions of the analysis, which suggests that high-order schemes can be used to improve empirical gradient estimates. The shape of the probability density functions is also found to be sensitive to the choice of numerical differentiation scheme. The effect of numerical differentiation is also discussed with respect to particle image velocimetry (PIV) measurements of a nominally two-dimensional planar mixing layer. It is found that the relatively low signal-to-noise ratio inherent in typical PIV measurements necessitates the use of low-order schemes to prevent excessive noise amplification, which increases with the order of the scheme. The results of the present work demonstrate that high-order numerical differentiation schemes can be employed to more accurately resolve gradients measured at a given resolution provided the measurements have an adequate signal-to-noise ratio.