Evolution of a lamellar domain structure for an equilibrating lyotropic liquid crystal

Aerosol OT/water exhibits a lamellar phase over a wide range of concentrations. We show, by magnetic resonance (NMR) and scanning electron microscopy (SEM), that the morphology of the lamellar phase varies significantly across that range and that the rate of equilibration depends strongly on concentration (25, 33, and 50 wt %) with, paradoxically, the faster equilibration at higher surfactant concentrations. We find that the 25 wt % sample exhibits a defect-rich local structure, characteristic of a superposed L(3) character. Further into the lamellar region, at 33 wt %, this defect-rich structure persists heterogeneously, while, at 50 wt %, the lamellar phase domains are highly ordered. The NMR methods used here included (2)H spectroscopy and the two-dimensional NMR method, diffusion-diffusion exchange spectroscopy (DEXSY). The latter was used to obtain quantitative information on the domain sizes and defects within the polydomain lamellar mesophase. Comparison of the NMR with the SEM results suggests that, at 25 wt % AOT, bilayer defects play an important role in influencing the (2)H NMR and DEXSY NMR results.     

Effects of radiation damping on Z-spectra

Radiation damping induced by the strong water magnetization in Z-spectroscopy experiments can be sufficient to perturb significantly the resultant Z-spectrum. With a probe tuned to exact electrical resonance the effects are relatively straightforward, narrowing the central feature of the Z-spectrum. Where, as is commonly the case, the probe is tuned sufficiently well to give optimum signal-to-noise ratio and radiofrequency field strength but is not at exact resonance, radiation damping introduces an unexpected asymmetry into the Z-spectrum. This has the potential to complicate the use of Z-spectrum asymmetry to study chemical exchange, for example in the estimation of pH in vivo.     

Stereoselective Synthesis of β-Glycinamide Ribonucleotide

A diastereoselective synthesis of the β-anomer of glycinamide ribonucleotide (β-GAR) has been developed. The synthesis was accomplished in nine steps from D-ribose and occurred in 5% overall yield. The route provided material on the multi-milligram scale. The synthetic β-GAR formed was remarkably resistant to anomerization both in solution and as a solid.     

Conductive Hydrogels: Mechanically Robust Hybrids for Use as Biomaterials

A hybrid system for producing conducting polymers within a doping hydrogel mesh is presented. These conductive hydrogels demonstrate comparable electroactivity to conventional conducting polymers without requiring the need for mobile doping ions which are typically used in literature. These hybrids have superior mechanical stability and a modulus significantly closer to neural tissue than materials which are commonly used for medical electrodes. Additionally they are shown to support the attachment and differentiation of neural like cells, with improved interaction when compared to homogeneous hydrogels. The system provides flexibility such that biologic incorporation can be tailored for application.

     

Impact of Substituents in Tumor Uptake and Fluorescence Imaging Ability of Near‐Infrared Cyanine‐like Dyes

This report presents a simple strategy to introduce various functionalities in a cyanine dye (bis‐indole‐N‐butylsulfonate‐polymethine bearing a fused cyclic chloro‐cyclohexene ring structure), and assess the impact of these substitutions in tumor uptake, retention and imaging. The results obtained from the structural activity relationship (SAR) study demonstrate that certain structural features introduced in the cyanine dye moiety make a remarkable difference in tumor avidity. Among the compounds investigated, the symmetrical CDs containing an amino‐phenyl thioether group attached to a cyclohexene ring system and the two N‐butyl linkers with terminal sulfonate groups in benzoindole moieties exhibited excellent tumor imaging ability in BALB/c mice bearing Colon26 tumors. Compared to indocyanine green (ICG), approved by FDA as a blood pooling agent, which has also been investigated for the use in tumor imaging, the modified CD selected on the basis of SAR study produced enhanced uptake and longer retention in tumor(s). A facile approach reported herein for introducing a variety of functionalities in tumor‐avid CD provides an opportunity to create multi‐imaging modality agent(s). Using a combination of mass spectrometry and absorbance techniques, the photobleaching of one of the CDs was analyzed and significant regioselective photooxidation was observed.     

False EX1 signatures caused by sample carryover during HX MS analyses

Discovery of EX1 kinetics in hydrogen exchange (HX) mass spectrometry (MS) experiments is rare. Proteins follow the EX1 kinetic regime when cooperative unfolding events simultaneously expose multiple residues to solvent such that they all become deuterated together before the region is able to refold. A number of factors can contribute to what we call "false EX1" in which it appears as though EX1 occurs in a protein when it probably does not. One of the contributors to false EX1 is peptide carryover between chromatographic runs. In this work, we explore the origins of peptide carryover in HX MS, describe how carryover causes mass spectra to indicate false EX1 kinetics and then describe an optimized washing protocol that can be used to eliminate peptide carryover. A series of solvent injections was developed and found to efficiently eliminate carryover signatures such that analysis of deuterium incorporation could be reliably followed for two proteins prone to high carryover.     

Subglottic Jet Ventilation for Suspension Microlaryngoscopy

High-frequency subglottic jet ventilation was used in 142 consecutive adults with grade I airways treated with suspension microlaryngoscopy. All cases were managed by the senior anesthesiologist (AP) and the large majority by the senior surgeon (JR), between 2000 and 2002. The laser was used in 30% of cases. There were few complications, none serious, associated with this technique in this series. The subglottic catheter never proved impossible to insert and only needed to be replaced by the supraglottic catheter in two patients because of limitation of visualization of the posterior glottis. The technique was used in a wide variety of surgical pathology from benign hyperfunction-related laryngeal pathology through paralytic vocal fold conditions through papilloma. Advantages and disadvantages over traditional intubation techniques and supraglottic jet ventilation are reviewed, including such issues as ease of intubation/ventilation, surgical exposure/control, maintenance of O2 and CO2 levels, and use in the limited/borderline airway.     

T2* measurements in human brain at 1.5, 3 and 7 T

Measurements have been carried out in six subjects at magnetic fields of 1.5, 3 and 7 T, with the aim of characterizing the variation of T2* with field strength in human brain. Accurate measurement of T2* in the presence of macroscopic magnetic field inhomogeneity is problematic due to signal decay resulting from through-slice dephasing. The approach employed here allowed the signal decay due to through-slice dephasing to be characterized and removed from data, thus facilitating an accurate measurement of T2* even at ultrahigh field. Using double inversion recovery turbo spin-echo images for tissue classification, an analysis of T2* relaxation times in cortical grey matter and white matter was carried out, along with an evaluation of the variation of T2* with field strength in the caudate nucleus and putamen. The results show an approximately linear increase in relaxation rate R2* with field strength for all tissues, leading to a greater range of relaxation times across tissue types at 7 T that can be exploited in high-resolution T2*-weighted imaging.