Paramagnetic transition metal carbonyls : IV. ESR study of anions derived from (CO)5MnPbPh3 and (CO)4CoPbPh3 by high energy radiation

Exposure of (CO)₅MnPbPh₃ to ⁶⁰Co γ-ray at 77 K gave one major paramagnetic species detectable by ESR spectroscopy. This exhibited an anisotropic hyperfine interaction with ⁵⁵Mn, near free-spin g-values, and a small, almost isotropic coupling to ²⁰⁷Pb. The form of the A(⁵⁵Mn) and g-tensor components suggest an orbital of d_z² symmetry on manganese for the unpaired electron, but this cannot be directed along the MnPb bond since the ²⁰⁷Pb hyperfine coupling indicates a very low spin-density on lead. We suggest that the centre is formed by electron addition to manganese to give a formal d⁷ centre, with concomitant loss of one equatorial carbonyl ligand. We defind z as the direction of the lost ligand. A second centre, detected at high gain, having a large hyperfine coupling to ²⁰⁷Pb and a 31 G coupling to ⁵⁵Mn is tentatively identified as the parent cation.In marked contrast, the molecule (CO)₄CoPbPh₃ gave a single centre having comparable ⁵⁹Co hyperfine and g-tensor components, but also a very large hyperfine coupling to ²⁰⁷Pb (ca. 3300 G). Thus, in this case, an electron gain centre (d⁹) has been formed, the electron being accomodated in the highest MO having a large d_z² component on cobalt (z being now the CoPb direction).Reasons for the adoption of these different structures are discussed.     

Enhanced stability and activity of temozolomide in primary glioblastoma multiforme cells with cucurbit[n]uril

Temozolomide (TMZ) is the primary chemotherapeutic agent for treatment of glioblastoma multiforme (GBM) yet it has a fast rate of degradation under physiological conditions to the 'active' MTIC, which has poor penetration of the blood-brain barrier and cellular absorption. Herein we have demonstrated binding of TMZ within the cavity of nano-container cucurbit[7]uril, resulting in a decreased rate of drug degradation. Prolonging the lifetime of the TMZ under physiological conditions through encapsulation dramatically improved the drug's activity against primary GBM cell lines as more TMZ could be absorbed by the cells before degradation. This work can potentially lead to increases in the drug's propensity for crossing the blood-brain barrier and absorption into the GBM cells, thereby increasing the efficacy of this chemotherapy.     

Single-step fabrication of patterned gold film array by an engineered multi-functional peptide

This study constitutes a demonstration of the biological route to controlled nano-fabrication via modular multi-functional inorganic-binding peptides. Specifically, we use gold- and silica-binding peptide sequences, fused into a single molecule via a structural peptide spacer, to assemble pre-synthesized gold nanoparticles on silica surface, as well as to synthesize nanometallic particles in situ on the peptide-patterned regions. The resulting film-like gold nanoparticle arrays with controlled spatial organization are characterized by various microscopy and spectroscopy techniques. The described bio-enabled, single-step synthetic process offers many advantages over conventional approaches for surface modifications, self-assembly and device fabrication due to the peptides' modularity, inherent biocompatibility, material specificity and catalytic activity in aqueous environments. Our results showcase the potential of artificially-derived peptides to play a key role in simplifying the assembly and synthesis of multi-material nano-systems in environmentally benign processes.     

EFFECTS OF LIGHT ON T-CELLS IN HIV-INFECTED SUBJECTS ARE NOT DEPENDENT ON HISTORY OF SEASONAL AFFECTIVE DISORDER

In order to evaluate the effect of light on helper- and suppressor-T-cell counts in HIV-infected individuals, with and without a history of seasonal affective disorder (SAD), we treated 35 subjects with 45 min of light therapy in the morning, in a crossover design involving two 2 week treatment conditions: visible white light (half-peak band width, 530-620 nm; 10 000 lux) and visible red light (half-peak band width, 615-685 nm; 175 lux). We found small but significant differences between the two treatment conditions, with higher CD4 and CD8 levels during the white, as compared with the red, condition. There were no differences between baseline and treatment conditions. Both light treatment conditions were associated with significant mood improvements in the SAD, but not the non-SAD, subjects. There was no evidence that the higher cell counts seen under the bright light conditions were mediated by the effects of light on mood or on plasma Cortisol levels. While the size of the light effect on T-cells renders questionable the potential therapeutic value of this treatment modality for HIV, the finding is of theoretical interest and is reassuring for those HIV-infected individuals who require light treatment for other reasons.     

Anatomy of the thyroarytenoid branch of the recurrent laryngeal nerve.

OBJECTIVE: To determine the position and anatomic variability of the thyroarytenoid (TA) branch of the recurrent laryngeal nerve (RLN). METHODS: The RLN on 13 human cadaver specimens (24 sides) was dissected to the termination of the TA branch in the TA muscle. A pin was placed at the inferior aspect of the thyroid cartilage at the inferior tubercle. Using a caliper, the distance from the pin to the TA branch of the RLN was measured. The direction of the nerve and number of branches were recorded. RESULTS: The average distance to the TA branch of the RLN is 4.23 mm with a standard deviation of 2.86 mm. The median distance is 3.75 mm. Most of the specimens fell in a range of 1 to 4 mm. Overall, 54% of the nerves traveled in a horizontal direction, but vertical and oblique orientations were observed. About 20% of specimens demonstrated branching of the TA nerve. CONCLUSION: Measuring 4 mm from the inferior tubercle along a perpendicular line from the thyroid tubercle on the inferior border of the thyroid cartilage provides a good estimate of the location of the TA branch of the RLN. This information is useful when creating a posterior thyrotomy for TA neurectomy for patients with adductor spasmodic dysphonia. Knowledge of the course and possible branching of the nerve, will aid in localizing the nerve as well as ensuring adequate resection.     

Dilatometric and electrochemical studies on hydrogen transport through RuO2 coated on palladium

Combined electrochemical and dilatometry measurements were used to characterize the transport of hydrogen through thin RuO₂ layers coated on palladium wire electrodes. Hydrogen dissolved in aqueous solutions penetrated through the oxide in a pH-dependent mechanism that combined diffusion of molecular hydrogen and pH-dependent proton hopping through redox sites within the oxide lattice. When cathodically charged, hydrogen was generated and absorbed at the oxide-solution interface only after Ru (IV) reduction occurs, and then, transported into the metal.     

Bullseye color schlieren flow visualization

In this variant of schlieren flow visualization a tricolored filter pattern made up of concentric rings is used instead of a knife edge at the cut-off plane. The method is particularly useful in combustion studies since it provides the range necessary to visualize flames while retaining the sensitivity necessary to detect fluid motion in the surrounding gasses. That utility is demonstrated in this paper in terms of basic principles and by application. Photographs presented include images of both premixed and diffusion flames in an unsteady swirling flow within a cylinder.     

The CellCard System: a novel approach to assessing compound selectivity for lead prioritization of G protein-coupled receptors

Advances in high throughput screening technologies have led to the identification of many small molecules, "hits", with activities toward the target of interest. And, as the screening technologies become faster and more robust, the rate at which the molecules are identified continues to increase. This evolution of high throughput screening technologies has generated a significant strain on the laboratories involved with the downstream profiling of these hits using cell-based assays. The CellCard System, by enabling multiple targets and/or cell lines to be assayed simultaneously within a single well, provides a platform on which selectivity screening can be quickly and robustly performed. Here we describe two case studies using the beta-lactamase and beta-galactosidase reporter gene systems to characterize G protein-coupled receptor agonist activity. Using these examples we demonstrate how the implementation of this technology enables assay miniaturization without micro-fluidic devices as well as how the inclusion of intra-well controls can provide a means of data quality assessment within each well.     

The electrical double layer of carbon and graphite electrodes: Part V. Specific interactions with simple ions

The specific interaction of halide and alkali metal ions with carbon and graphite electrodes was investigated by monitoring the dimensional changes and the charging current during a linear potential scan. The potential of zero charge (pzc), as detected by a minimum in the length vs. potential curve, is shifted towards more negative values when a larger halide is the anion in a single electrolyte solution and as the solution concentration increases. This is interpreted in terms of increasing specific interactions. Alkali cations, on the other hand, do not exhibit any measurable effects of specific interaction,The differential capacity of both carbon and graphite increases due to specific interactions. However, the contribution to the capacity of the carbon is much larger than that for the graphite. This is interpreted on the basis of the much larger contribution of the edge planes in the carbon.