Microrheology of aggregated emulsion droplet networks, studied with AFM-CSLM

We studied the mechanical behavior of densely packed (up to approximately 30% v/v), sedimented layers of (1 microm) water-in-oil W/O emulsion droplets, upon indentation with a (10 microm) large spherical probe. In the presence of attractive forces, the droplets form solid like networks which can resist deformation. Adding a polymer to the oil phase was used to control droplet attraction. The droplet layers were assembled via normal gravity settling. Considering that both the network structure and the droplet interactions play a key role, we used a combination of atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM) to characterize the mechanical behavior. Here the AFM was used both as indentation tool and as force sensor. Indentation experiments were performed via a protocol consisting of approach, waiting, and retract stages. CSLM was used to observe the network structure at micron resolution in real time. Use of refractive index matched fluorescent droplets allowed the visualization of the entire layer. Upon compression with the probe, a markedly nonhomogeneous deformation occurred, evidenced by the formation of a dense corona (containing practically all of the displaced droplets) in the direct vicinity of the probe, as well as more subtle deformations of force-chains at larger distances. Upon decompression, both the imprint of the indenter and the corona remained, even long after the load was released. The force-distance curves recorded with the AFM correspond well to these observations. For each deformation cycle performed on fresh material, the retract curve was much steeper than the approach curve, thus corroborating the occurrence of irreversible compaction. Contrary to classic linear viscoelastic materials, this hysteresis did not show any dependence on the deformation speed. Our force-indentation approach curves were seen to scale roughly as F approximately delta(3/2). The pre-factor was found to increase with the polymer concentration and with the density of the network. These findings suggest that this new AFM-CSLM method could be used for rheological characterization of small volumes of "granular networks" in liquid. Our hypothesis that the mechanical resistance of the networks originates from interdroplet friction forces, which in turn are set by the interdroplet potential forces, is supported by the predictions from a new mechanical model in which the interdroplet bonds are represented by stick-slip elements.     

Azaxanthones and azathioxanthones are effective sensitisers for europium and terbium luminescence

Several azaxanthone and azathioxanthone sensitising chromophores have been incorporated into macrocyclic ligands and form well-defined Eu and Tb complexes in polar media. Excitation of the heterocyclic chromophore in the range 330 to 382 nm leads to modest amounts of aromatic fluorescence and relatively efficient metal-based luminescence, with absolute metal-based quantum yields of up to 24% in aqueous media.     

In-source CID of guanosine: Gas phase ion-molecule reactions

In-source collision induced dissociation was applied to access second generation ions of protonated guanosine. The in-source gas-phase behavior of [BH2]+-NH3 (m/z 135, C5H3N4O+) was investigated. Adduct formation and reactions with available solvent molecules (H2O and CH3OH) were demonstrated. Several addition/elimination sequences were observed for this particular ion and solvent molecules. Dissociation pathways for the newly formed ions were developed using a QqTOF mass spectrometer, permitting the assignment of elemental compositions of all product ions produced. Reaction schemes were suggested arising from the ring-opened intermediate of the protonated base moiety [BH2]+, obtained from fragmentation of guanosine. The mass spectral data revealed that the in-source CH3OH-reaction product underwent more complex fragmentations than the comparable ion following reaction with H2O. A rearrangement and a parallel radical dissociation pathway were discerned. Apart from the mass spectrometric evidence, the fragmentation schemes are supported by density functional theory calculations, in which the reaction of the ring-opened protonated guanine intermediate with CH3OH and a number of subsequent fragmentations were elaborated. Additionally, an in-source transition from the ring-opened intermediate of protonated guanine to the ring-opened intermediate of protonated xanthine was suggested. For comparison, a low-energy collision induced dissociation study of xanthosine was performed. Its dissociation pathways agreed with our assumption.     

Enantiomeric separation of omeprazole and its metabolite 5-hydroxyomeprazole using non-aqueous capillary electrophoresis

This study demonstrates the development and validation of a non-aqueous capillary electrophoresis (NACE) method for enantiomeric determination of omeprazole and its metabolite 5-hydroxyomeprazole. Heptakis-(2,3-di-O-methyl-6-O-sulfo)-beta-cyclodextrin (HDMS-beta-CD) was chosen as the chiral selector in an ammonium acetate buffer acidified with formic acid in methanol. Parameters such as CD concentration, concentration of buffer electrolyte, voltage and temperature were studied in order to optimize both the enantioresolution and migration times. An experimental design was utilized for method optimization, using software Modde 5.0. Validation of the developed method showed good linearity, which was tested over a concentration range of 2.5-500 microM. The regression coefficients for S-omeprazole, S-5-hydroxyomeprazole, R-omeprazole and R-5-hydroxyomeprazole were between 0.996 and 0.997. The limits of detection for the four enantiomers were in the range from 45 to 51microM and the limits of quantification were between 149 and 170 microM with UV detection at 301nm. Using a reduced temperature of 16 degrees C gave improved resolution values, reproducibility and also decreased the occurrence of current loss within the capillary. RSD values for peak migration time were calculated to be between 0.41 and 1.48% using an inter-day study.     

Modeling auditory evoked brainstem responses to transient stimuli

A quantitative model is presented that describes the formation of auditory brainstem responses (ABRs) to tone pulses, clicks, and rising chirps as a function of stimulation level. The model computes the convolution of the instantaneous discharge rates using the "humanized" nonlinear auditory-nerve model of Zilany and Bruce [J. Acoust. Soc. Am. 122, 402-417 (2007)] and an empirically derived unitary response function which is assumed to reflect contributions from different cell populations within the auditory brainstem, recorded at a given pair of electrodes on the scalp. It is shown that the model accounts for the decrease of tone-pulse evoked wave-V latency with frequency but underestimates the level dependency of the tone-pulse as well as click-evoked latency values. Furthermore, the model correctly predicts the nonlinear wave-V amplitude behavior in response to the chirp stimulation both as a function of chirp sweeping rate and level. Overall, the results support the hypothesis that the pattern of ABR generation is strongly affected by the nonlinear and dispersive processes in the cochlea.     

Graphs that admit right angle crossing drawings

We consider right angle crossing (RAC) drawings of graphs in which the edges are represented by polygonal arcs and any two edges can cross only at a right angle. We show that if a graph with n vertices admits a RAC drawing with at most 1 bend or 2 bends per edge, then the number of edges is at most 6.5n and 74.2n, respectively. This is a strengthening of a recent result of Didimo et al.     

Beyond Millikan: the dynamics of charging events on individual colloidal particles

By measuring the stable charge on oil drops in air, Millikan demonstrated the discrete nature of electric charge. We extend his approach to the charge on solid-liquid interfaces, and focus on the dynamics of the discrete fluctuations. Our measurements are accurate and fast enough to observe changes of one elementary charge. Experiments over thousands of seconds yield information about the fast dynamics of electrochemical reactions, relevant for physicochemical and biological systems. As an example, we study (dis)charging processes on colloidal particles in a nonpolar liquid.     

CIEF separation,UV detection,and quantification of ampholytic antibiotics and bacteria from different matrices

The effect of antibiotics on the microbial cells and concentration of antibiotics in the human body is essential for the effective use of antimicrobial therapy. The capillary isoelectric focusing is a suitable technique for the separation and the detection of bacteria, and amphoteric substances from nature. However, the determination of isoelectric points of ampholytic antibiotics by conventional techniques is time consuming. For this reason, capillary isoelectric focusing seems to be appropriate as a simple and reliable way for establishing them. The separation conditions for the capillary isoelectric focusing of selected ampholytic antibiotics with known isoelectric points and pK _as, ampicillin (pI 4.9), ciprofloxacin (pI 7.4), ofloxacin (pI 7.1), tetracycline (pI 5.4), tigecycline (pI 9.7), and vancomycin (pI 8.1), were found and optimized in the suitable pH ranges pH 2.0–5.3, 2.0–9.6, and 9.0–10.4. The established values of isoelectric points correspond with those found in the literature except tigecycline. Its pI was not found in the literature. As an example of a possible procedure for direct detection of both ampholytic antibiotics and bacteria, Staphylococcus epidermidis, in the presence of culture media or whole human blood, was found. The changes of the bacterial cells after their treatment with tetracycline were confirmed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Capillary isoelectric focusing allows the fast and simple determination of isoelectric points of relevant antibiotics, their quantification from the environment, as well as studying their effectiveness on microorganisms in biological samples. Graphical Abstract

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From NMP to RAFT and Thiol‐Ene Chemistry by In Situ Functionalization of Nitroxide Chain Ends

A straightforward, novel strategy based on the in situ functionalization of polymers prepared by nitroxide‐mediated polymerization (NMP), for the use as an extension toward block copolymers and post‐polymerization modifications, has been investigated. The nitroxide end group is exchanged for a thiocarbonylthio end group by a rapid transfer reaction with bis(thiobenzoyl) disulfide to generate in situ reversible addition–fragmentation chain transfer (RAFT) macroinitiators. Moreover, not only have these macroinitiators been used in chain extension and block copolymerization experiments by the RAFT process but also a thiol‐terminated polymer is synthesized by aminolysis of the RAFT end group and subsequently reacted with dodecyl vinyl ether by thiol‐ene chemistry.