Eumelanin Graphene-Like Integration: The Impact on Physical Properties and Electrical Conductivity

The recent development of eumelanin pigment-based blends integrating "classical" organic conducting materials is expanding the scope of eumelanin in bioelectronics. Beyond the achievement of high conductivity level, another major goal lays in the knowledge and feasible control of structure/properties relationship. We systematically investigated different hybrid materials prepared by in situ polymerization of the eumelanin precursor 5,6-dihydroxyindole (DHI) in presence of various amounts of graphene-like layers. Spectroscopic studies performed by solid state nuclear magnetic resonance (ss-NMR), x-ray photoemission, and absorption spectroscopies gave a strong indication of the direct impact that the integration of graphene-like layers into the nascent polymerized DHI-based eumelanin has on the structural organization of the pigment itself, while infrared, and photoemission spectroscopies indicated the occurrence of negligible changes as concerns the chemical units. A tighter packing of the constituent units could represent a strong factor responsible for the observed improved electrical conductivity of the hybrid materials, and could be possible exploited as a tool for electrical conductivity tuning

Fluorescence kinetics of flavin adenine dinucleotide in different microenvironments

Fluorescence kinetics of flavin adenine dinucleotide was measured in a wide time and spectral range in different media, affecting its intra- end extramolecular interactions, and analyzed by a new method based on compressed sensing

Compressional behaviour of paulingite -A sub-nanosponge?

Introduction Paulingite is a rare zeolite, found in vesicles in basalt flows, with ideal chemical formula: (K,Na,Ca0.5,Ba0.5,)10(Al10Si32O84)\uf0d730H2O (Z = 16). Its crystal structure was solved and refined by Gordon et al. (1966) in the space group Im3m, showing the complex framework topology of this zeolite designated with the IZA-code \u201cPAU\u201d. A structural re-investigation was carried out later by Lengauer et al. (1997). The tetrahedral framework topology of paulingite is characterized by a connecting double 8-ring (D8R), which links alternatively the \uf061-cage (truncated cuboctahedron) and the \uf067-cage (gmelinite-type cage). The D8R, the \uf061-cage and the \uf067-cage represent the building-block units of the PAU framework. The main voids systems of the PAU framework are represented by two parallel (and independent) sets of a three-dimensional channel systems oriented along the principal axes and shifted \ubd, \ubd, \ubd against each other. Along the threefold axis of the PAU framework, a second type of a channel system exists, which is built up by the \uf061-cage and a modified form of the levyne-cage only observed in the paulingite topology (i.e., \uf070-cage) (Lengauer et al. 1997). The PAU framework type is considered as one of the most complex in the mineral world. In all the structure refinements so far reported, the Si/Al-distribution was modelled as completely disordered. A series of extra-framework sites were located. The long \u201cfree diameters\u201d of the channel systems make this zeolite a good candidate to explore the P-induced penetration of external molecular species in response to hydrostatic compression (e.g., Gatta 2008, 2010). Experimental Methods A sample of paulingite from Vina\u159ick\ue1 hora Hill near Kladno (Czech Republic) was used for our experiments. A sample from the same locality was previously used by Lengauer et al. (1997) for their chemical and crystallographic study. Electron microprobe analysis (in wavelength dispersive mode) along with thermo-gravimetric data yielded the following chemical formula: (Ca2.57K2.28Ba1.39Na0.38)(Alll.55Si30.59O84)x 27H2O (Lengauer et al. 1997). A single-crystal of paulingite, free of defects under polarized microscope, was selected for the in-situ diffraction experiment with a diamond anvil cell (DAC). Intensity diffraction data were first collected at room-conditions with a Stoe StadiVari diffractometer with an high-brilliance Incoatec Mo I\ub5s X-ray-source and a Dectris Pilatus 300K pixel detector. The structure refinement was performed in the space group Im3m using the structural model of Lengauer et al. (1997) to a R1 = 0.0802 for 2477 Fo > 4\uf073(Fo) and 255 refined parameters. The same crystal was used for the high-pressure (HP) experiment performed using an ETH-type DAC. The experiment was conducted using a mixture of methanol:ethanol = 4:1 as hydrostatic P-transmitting medium, along with a few ruby chips serving as P-calibrant. Unit-cell parameters were measured between 0.0001 (crystal in the DAC with no pressure medium) and 3.3(1) GPa. Two further in-situ HP synchrotron X-ray powder diffraction experiments were performed at the X7A beamline at the national synchrotron light source (NSLS) at Brookhaven National Laboratory (BNL). A gas-proportional position-sensitive detector was used. The wavelength of the incident beam was 0.60046(1) \uc5 as determined from a CeO2 standard. A modified Merrill\u2013Bassett DAC was used to generate HP-conditions. Two compression experiments with two different P-fluids were performed, i.e., with silicon-oil and a mix of methanol:ethanol:water = 16:3:1. The evolution of the cell parameters with P for all three pressure-transmitting media is shown in Fig. 1. Results and Discussion The evolution of the unit-cell parameters of paulingite with P based on our experiments with different P-media show a dramatic role played by the compression-fluid on the behavior of this zeolite (Figure 1). Due to its polymeric nature, silicon-oil can be unambiguously considered as a \u201cnon-penetrating\u201d P-medium. The compressional pattern obtained with silicon-oil describes the actual elastic behavior of paulingite (i.e., without any interference of the P-fluid). The Birch-Murnaghan equation of state truncated to the second-order was used to fit the experimental P-V data within the P-range investigated (i.e. 0.0001-2.5(1) GPa), giving the following isothermal bulk modulus: K0 = \uf0620-1 = V0(\uf0b6P/\uf0b6V) = 18(1) GPa (\uf0620 = 0.055(3) GPa-1). Paulingite appears to be one of the softest crystalline inorganic materials reported so far. The HP-data obtained using the mix methanol:ethanol = 4:1 and methanol:ethanol:water = 16:3:1 suggest that these molecules act as \u201cpenetrating\u201d media in response to the applied pressure. The P-induced penetration of external molecules through the cavities leads to a lower bulk compressibility of paulingite. The different compressibility of paulingite in methanol:ethanol = 4:1 and methanol:ethanol:water = 16:3:1 mix reflects the different penetrability of the media. Water is clearly the most penetrating molecule in response to the applied pressure, and so in general an hydrous medium tends to decrease significantly the compressional pattern of a porous material (Gatta 2008, 2010). Interestingly, the P-induced penetration of external molecules in paulingite structure does not lead to spectacular expansion (with a drastic discontinuity in the P-V behaviour), as observed for example in natrolite (Lee et al. 2002). The complexity of the paulingite structure did not allow to perform structure refinement at high pressure, hindering a description of the penetration mechanisms at the atomic scale. A series of further experiments are in progress in order to explore: 1) the reversibility of the P-induced penetration of aforementioned molecules and 2) the behavior of this zeolite as a \u201csub-nanosponge\u201d for other small molecules in response to hydrostatic pressure. Acknowledgment GDG acknowledges the Italian Ministry of Education, MIUR-Project: \u201cFuturo in Ricerca 2012 - ImPACT- RBFR12CLQD\u201d. References Gatta, G.D. (2008) Does porous mean soft? On the elastic behaviour and structural evolution of zeolites under pressure. Zeitschrift f\ufcr Kristallographie, 223, 160\u2013170. Gatta, G.D. (2010) Extreme deformation mechanisms in open-framework silicates at high-pressure: Evidence of anomalous inter-tetrahedral angles. Microporous and Mesoporous Materials, 128, 78\u201384. Gordon, E.K., Samson, S. and Kamb, W.B. (1966). Crystal structure of the zeolite paulingite. Science, 154, 1004-1007. Lee, Y., Vogt, T., Hriljac, J.A., Parise, J.B., and Artioli, G. (2002) Pressure-Induced Volume Expansion of Zeolites in the Natrolite Family. Journal of the American Chemical Society, 124, 5466-5475. Lengauer, C.L., Giester, G., and Tillmanns, E. (1997). Mineralogical characterization of paulingite from Vinarick\ue1 Hora, Czech Republic. Mineralogical Magazine, 61, 591-606

Temporal trends in mode, site and stage of presentation with the introduction of colorectal cancer screening: a decade of experience from the West of Scotland

background:  Population colorectal cancer screening programmes have been introduced to reduce cancer-specific mortality through the detection of early-stage disease. The present study aimed to examine the impact of screening introduction in the West of Scotland. methods:  Data on all patients with a diagnosis of colorectal cancer between January 2003 and December 2012 were extracted from a prospectively maintained regional audit database. Changes in mode, site and stage of presentation before, during and after screening introduction were examined. results:  In a population of 2.4 million, over a 10-year period, 14 487 incident cases of colorectal cancer were noted. Of these, 7827 (54%) were males and 7727 (53%) were socioeconomically deprived. In the postscreening era, 18% were diagnosed via the screening programme. There was a reduction in both emergency presentation (20% prescreening vs 13% postscreening, P0.001) and the proportion of rectal cancers (34% prescreening vs 31% pos-screening, P0.001) over the timeframe. Within non-metastatic disease, an increase in the proportion of stage I tumours at diagnosis was noted (17% prescreening vs 28% postscreening, P0.001). conclusions:  Within non-metastatic disease, a shift towards earlier stage at diagnosis has accompanied the introduction of a national screening programme. Such a change should lead to improved outcomes in patients with colorectal cancer

Divergent mathematical treatments in utility theory

In this paper I study how divergent mathematical treatments affect mathematical modelling, with a special focus on utility theory. In particular I examine recent work on the ranking of information states and the discounting of future utilities, in order to show how, by replacing the standard analytical treatment of the models involved with one based on the framework of Nonstandard Analysis, diametrically opposite results are obtained. In both cases, the choice between the standard and nonstandard treatment amounts to a selection of set-theoretical parameters that cannot be made on purely empirical grounds. The analysis of this phenomenon gives rise to a simple logical account of the relativity of impossibility theorems in economic theory, which concludes the paper

Single cell metabolic imaging of tumor and immune cells in vivo in melanoma bearing mice

IntroductionMetabolic reprogramming of cancer and immune cells occurs during tumorigenesis and has a significant impact on cancer progression. Unfortunately, current techniques to measure tumor and immune cell metabolism require sample destruction and/or cell isolations that remove the spatial context. Two-photon fluorescence lifetime imaging microscopy (FLIM) of the autofluorescent metabolic coenzymes nicotinamide adenine dinucleotide (phosphate) (NAD(P)H) and flavin adenine dinucleotide (FAD) provides in vivo images of cell metabolism at a single cell level.MethodsHere, we report an immunocompetent mCherry reporter mouse model for immune cells that express CD4 either during differentiation or CD4 and/or CD8 in their mature state and perform in vivo imaging of immune and cancer cells within a syngeneic B78 melanoma model. We also report an algorithm for single cell segmentation of mCherry-expressing immune cells within in vivo images.ResultsWe found that immune cells within B78 tumors exhibited decreased FAD mean lifetime and an increased proportion of bound FAD compared to immune cells within spleens. Tumor infiltrating immune cell size also increased compared to immune cells from spleens. These changes are consistent with a shift towards increased activation and proliferation in tumor infiltrating immune cells compared to immune cells from spleens. Tumor infiltrating immune cells exhibited increased FAD mean lifetime and increased protein-bound FAD lifetime compared to B78 tumor cells within the same tumor. Single cell metabolic heterogeneity was observed in both immune and tumor cells in vivo.DiscussionThis approach can be used to monitor single cell metabolic heterogeneity in tumor cells and immune cells to study promising treatments for cancer in the native in vivo context

Comprehensive histopathological comparison of epidermotropic/dermal metastatic melanoma and primary nodular melanoma

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141829/1/his13384.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141829/2/his13384_am.pd

G4-Quartet·M+Borate Hydrogels

The ability to modulate the physical properties of a supramolecular hydrogel may be beneficial for biomaterial and biomedical applications. We find that guanosine (G 1), when combined with 0.5 equiv of potassium borate, forms a strong, self-supporting hydrogel with elastic moduli >10 kPa. The countercation in the borate salt (MB(OH)4) significantly alters the physical properties of the hydrogel. The gelator combination of G 1 and KB(OH)4 formed the strongest hydrogel, while the weakest system was obtained with LiB(OH)4, as judged by 1H NMR and rheology. Data from powder XRD, 1H double-quantum solid-state magic-angle spinning (MAS) NMR and small-angle neutron scattering (SANS) were consistent with a structural model that involves formation of borate dimers and G4·K+ quartets by G 1 and KB(OH)4. Stacking of these G4·M+ quartets into G4-nanowires gives a hydrogel. We found that the M+ cation helps stabilize the anionic guanosine-borate (GB) diesters, as well as the G4-quartets. Supplementing the standard gelator mixture of G 1 and 0.5 equiv of KB(OH)4 with additional KCl or KNO3 increased the strength of the hydrogel. We found that thioflavin T fluoresces in the presence of G4·M+ precursor structures. This fluorescence response for thioflavin T was the greatest for the K+ GB system, presumably due to the enhanced interaction of the dye with the more stable G4·K+ quartets. The fluorescence of thioflavin T increased as a function of gelator concentration with an increase that correlated with the system’s gel point, as measured by solution viscosit

Porcine liver vascular bed in Biodur E20 corrosion casts

Background: Pigs are frequently used as animal models in experimental medicine. To identify processes of vascular development or regression, vascular elements must be recognised and quantified in a three-dimensional (3D) arrangement. Vascular corrosion casts enable the creation of 3D replicas of vascular trees. The aim of our study was to identify suitable casting media and optimise the protocol for porcine liver vascular corrosion casting. Materials and methods: Mercox II® (Ladd Research, Williston, Vermont, USA) and Biodur E20® Plus (Biodur Products, Heidelberg, Germany) were tested in 4 porcine livers. The resins (volume approximately 700 mL) were injected via the portal vein. Corrosion casts were examined by macro-computed tomography, micro-computed tomography and scanning electron microscopy. Results: For hepatectomies, the operating protocol was optimised to avoid gas or blood clot embolisation. We present a protocol for porcine liver vascular bed casting based on corrosion specimens prepared using Biodur E20® epoxy resin. Conclusions: Only Biodur E20®Plus appeared to be suitable for high-volume vascular corrosion casting due to its optimal permeability, sufficient processing time and minimum fragility. Biodur E20® Plus is slightly elastic, radio-opaque and alcohol-resistant. These properties make this acrylic resin suitable for not only vascular research but also teaching purposes.