Magnetic field induced assembly of highly ordered two-dimensional particle arrays

Suspended magnetic beads are exposed to an external homogeneous magnetic field which rotates around the axis perpendicular to the field direction. Because of dipolar interactions, magnetic beads assemble in highly ordered two-dimensional hexagonal arrays perpendicular to the rotation axis. By continuous provision of the particle concentration, the growth modes of two-dimensional particle clusters and monolayers are observed. The structure of the resulting assembled objects is analyzed for different field frequencies and particle concentrations. We identify dynamic processes which enhance stability and reduce lattice distortions and, thus, allow for the application of these particle agglomerations as dynamic components in lab-on-a-chip technologies.     

Tunable external cavity quantum cascade laser for the simultaneous determination of glucose and lactate in aqueous phase

A room temperature operated pulsed external-cavity (EC) quantum cascade laser (QCL) was used for mid-infrared (mid-IR) transmission measurements of glucose and lactate in aqueous solution. The high spectral power density of the EC-QCL (ranging from 1-350 mW) over a wide tuning range (1030-1230 cm(-1)) allowed transmission measurements through optical paths of 130 μm and more. This is a significant improvement in terms of robustness of the measurement setup, especially when samples containing cells or other particles, as is the case for biofluids, are to be analyzed. The broad tuning range furthermore permitted multi-analyte detection based on multivariate calibrations. Promising results on the simultaneous determination of glucose (c = 0-800 mg dL(-1)) and sodium-lactate (c = 0-224 mg dL(-1)) in aqueous solutions in the presence of the interferents maltose and xylose are reported. A partial least squares (PLS) calibration model was calculated which was able to predict the glucose concentration with a root mean square error of prediction (RMSEP) of 9.4 mg dL(-1), as proved by external validation. Due to their small size and room temperature operation, EC-QCLs offer an attractive alternative regarding the way mid-IR measurements are carried out. This may be of special importance for new reagent-free bedside monitoring systems.     

Can Copper(II) Mediate Hoogsteen Base‐Pairing in a Left‐Handed DNA Duplex? A Pulse EPR Study

Pulse EPR spectroscopy is used to investigate possible structural features of the copper(II) ion coordinated to poly(dG‐dC)?poly(dG‐dC) in a frozen aqueous solution, and the structural changes of the polynucleotide induced by the presence of the metal ion. Two different copper species were identified and their geometry explained by a molecular model. According to this model, one species is exclusively coordinated to a single guanine with the N7 nitrogen atom forming a coordinative bond with the copper. In the other species, a guanine and a cytosine form a ternary complex together with the copper ion. A copper crosslink between the N7 of guanine and N3 of cytosine is proposed as the most probable coordination site. Moreover, no evidence was found for an interaction of either copper species with a phosphate group or equatorial water molecules. In addition, circular dichroism (CD) spectroscopy showed that the DNA of the Cu^II‐poly(dG‐dC)?poly(dG‐dC) adducts resembles the left‐handed Z‐form. These results suggest that metal‐mediated Hoogsteen base pairing, as previously proposed for a right‐handed DNA duplex, can also occur in a double‐stranded left‐handed DNA.     

Redox cycling in nanofluidic channels using interdigitated electrodes

Amperometric detection is ideally suited for integration into micro- and nanofluidic systems as it directly yields an electrical signal and does not necessitate optical components. However, the range of systems to which it can be applied is constrained by the limited sensitivity and specificity of the method. These limitations can be partially alleviated through the use of redox cycling, in which multiple electrodes are employed to repeatedly reduce and oxidize analyte molecules and thereby amplify the detected signal. We have developed an interdigitated electrode device that is encased in a nanofluidic channel to provide a hundred-fold amplification of the amperometric signal from paracetamol. Due to the nanochannel design, the sensor is resistant to interference from molecules undergoing irreversible redox reactions. We demonstrate this selectivity by detecting paracetamol in the presence of excess ascorbic acid. Figure  

Barbituric acid as a substituent at aryl methylium ions

Activation of different benzophenone derivatives with triflic anhydride for electrophilic aromatic substitution of 5-phenylbarbituric acids leads to regioselective formation of the ortho-substituted product. The resulting triphenylmethylium salt can be isolated when the Michlers ketone is used. More electrophilic cations form cyclic enol ethers such as 1-n-butyl-9,9-diaryl-1,9-dihydro-10-oxa-1,3-diazaphenanthrene-2,4-diones. Alternatively, supramolecular complex formation with 2,6-diacetamido pyridine as well as carbenium ion generation have been studied. Although in dilute acid only protonation of one of the carbonyl oxygens occurs, ring opening of the cyclic enol ether toward the carbenium ion is observed in 96% sulfuric acid.     

Experimental and theoretical study of the coordination of 1,2,4-triazolato, tetrazolato, and pentazolato ligands to the [K(18-crown-6)]+ fragment

Treatment of 3,5-diisopropyltriazole, 3,5-diphenyltriazole, 3,5-di-3-pyridyltriazole, phenyltetrazole, pyrrolidinyltetrazole, or tert-butyltetrazole with equimolar quantities of potassium hydride and 18-crown-6 in tetrahydrofuran at ambient temperature led to slow hydrogen evolution and formation of (3,5-diisopropyl-1,2,4-triazolato)(18-crown-6)potassium (88%), (3,5-diphenyl-1,2,4-triazolato)(tetrahydrofuran)(18-crown-6)potassium (87%), (3,5-di-3-pyridyl-1,2,4-triazolato)(18-crown-6)potassium (81%), (phenyltetrazolato)(18-crown-6)potassium (94%), (pyrrolidinyltetrazolato)(18-crown-6)potassium (90%), and (tert-butyltetrazolato)(18-crown-6)potassium (94%) as colorless crystalline solids. (1,2,4-Triazolato)(18-crown-6)potassium was isolated as a hemi-hydrate in 81% yield upon treatment of 1,2,4-triazole with potassium metal in tetrahydrofuran. The X-ray crystal structures of these new complexes were determined, and the solid-state structures consist of the nitrogen heterocycles bonded to the (18-crown-6)potassium cationic fragments with eta2-bonding interactions. In addition, (3,5-diphenyl-1,2,4-triazolato)(tetrahydrofuran)(18-crown-6)potassium has one coordinated tetrahydrofuran ligand on the same face as the 3,5-diphenyl-1,2,4-triazolato ligand, while (3,5-di-3-pyridyl-1,2,4-triazolato)(18-crown-6)potassium forms a polymeric solid through coordination of the distal 3-pyridyl nitrogen atoms to the potassium ion on the face opposite the 1,2,4-triazolato ligand. The solid-state structures of the new complexes show variable asymmetry in the potassium-nitrogen distances within the eta2-interactions and also show variable bending of the heterocyclic C2N3 and CN4 cores toward the best plane of the 18-crown-6 ligand oxygen atoms. Molecular orbital and natural bond order calculations were carried out at the B3LYP/6-311G(d,p) level of theory on the model complex, (phenyltetrazolato)(18-crown-6)potassium, and demonstrate that the asymmetric potassium-nitrogen distances and bending of the CN4 core toward the 18-crown-6 ligand are due to hydrogen bond-like interactions between filled nitrogen-based orbitals and carbon-hydrogen sigma orbitals on the 18-crown-6 ligands. Calculations carried out on the model pentazolato complex (pentazolato)(18-crown-6)potassium predict a structure in which the pentazolato ligand N5 core is bent by 45 degrees toward the best plane of the 18-crown-6 oxygen atoms. Such bending is induced by the formation of intramolecular nitrogen-hydrogen-carbon hydrogen bonds. Examination of the solid-state structures of the new complexes reveals many intramolecular and intermolecular nitrogen-hydrogen distances of < or =3.0 A which support the presence of nitrogen-hydrogen-carbon hydrogen bonds.     

Lagrangian submanifolds and moment convexity

We consider a Hamiltonian torus action on a compact connected symplectic manifold and its associated momentum map . For certain Lagrangian submanifolds we show that is convex. The submanifolds arise as the fixed point set of an involutive diffeomorphism which satisfies several compatibility conditions with the torus action, but which is in general not anti-symplectic. As an application we complete a symplectic proof of Kostant's non-linear convexity theorem.

     

Synthesis of 1,2-dihydropyridines using vinyloxiranes as masked dienolates in imino-aldol reactions

[reaction: see text] The application of vinyloxiranes, substituted with an electron-withdrawing group, as masked dienolates in vinylogous imino-aldol reactions was achieved. Under the reaction conditions highly substituted 1,2-dihydropyridines were obtained in moderate to good yields. Mechanistic studies indicate that the reaction proceeds via the formation of an (E)-amino-alpha,beta-unsaturated aldehyde, followed by isomerization to the (Z)-isomer, cyclization, and elimination of a water molecule, leading to the formation of the 1,2-dihydropyridine.     

In situ broadband pulse compression for multiphoton microscopy using a shaper-assisted collinear SPIDER

The characterization and control of the phase of broadband femtosecond pulses in nonlinear microscopy are successfully demonstrated with a collinear configuration of spectral shear interferometry for direct electric field reconstruction (SPIDER). A femtosecond-pulse shaper is used as a dispersionless interferometer for the measurement of the spectral phase and to actively compress a broadband supercontinuum from a photonic crystal fiber. This allows in situ online phase management and enables the application of quantum control spectroscopy in microenvironments.