Does Pelletizing Catalysts Influence the Efficiency Number of Activity Measurements? Spectrochemical Engineering Considerations for an Accurate Operando Study

International audienc

Electronic structure and optical properties of ZnS/CdS nanoheterostructures

The electronic and optical properties of spherical nanoheterostructures are studied within the semi-empirical $sp^{3}s^{*}$ tight-binding model including the spin-orbit interaction. We use a symmetry-based approach previously applied to CdSe and CdTe quantum dots. The complete one-particle spectrum is obtained by using group-theoretical methods. The excitonic eigenstates are then deduced in the configuration-interaction approach by fully taking into account the Coulomb direct and exchange interactions. Here we focus on ZnS/CdS, ZnS/CdS/ZnS and CdS/ZnS nanocrystals with particular emphasis on recently reported experimental data. The degree of carrier localization in the CdS well layer is analyzed as a function of its thickness. We compute the excitonic fine structure, i.e., the relative intensities of low-energy optical transitions. The calculated values of the absorption gap show a good agreement with the experimental ones. Enhanced resonant photoluminescence Stokes shifts are predicted.Comment: 6 pages, 4 Figures, revtex

Unravelling the proteomic landscape of extracellular vesicles in prostate cancer by density-based fractionation of urine

Extracellular vesicles (EV) are increasingly being recognized as important vehicles of intercellular communication and promising diagnostic and prognostic biomarkers in cancer. Despite this enormous clinical potential, the plethora of methods to separate EV from biofluids, providing material of highly variable purity, and lacking knowledge regarding methodological repeatability pose a barrier to clinical translation. Urine is considered an ideal proximal fluid for the study of EV in urological cancers due to its direct contact with the urogenital system. We demonstrate that density-based fractionation of urine by bottom-up Optiprep density gradient centrifugation separates EV and soluble proteins with high specificity and repeatability. Mass spectrometry-based proteomic analysis of urinary EV (uEV) in men with benign and malignant prostate disease allowed us to significantly expand the known human uEV proteome with high specificity and identifies a unique biological profile in prostate cancer not uncovered by the analysis of soluble proteins. In addition, profiling the proteome of EV separated from prostate tumour conditioned medium and matched uEV confirms the specificity of the identified uEV proteome for prostate cancer. Finally, a comparative proteomic analysis with uEV from patients with bladder and renal cancer provided additional evidence of the selective enrichment of protein signatures in uEV reflecting their respective cancer tissues of origin. In conclusion, this study identifies hundreds of previously undetected proteins in uEV of prostate cancer patients and provides a powerful toolbox to map uEV content and contaminants ultimately allowing biomarker discovery in urological cancers

Exciton states and optical properties of CdSe nanocrystals

The optical spectra of CdSe nanocrystals up to 55 A in diameter are analyzed in a wide range of energies from the fine structure of the low-energy excitations to the so-called high-energy transitions. We apply a symmetry-based method in two steps. First we take the tight-binding (TB) parameters from the bulk sp^{3}s^{*} TB model, extended to include the spin-orbit interaction. The full single-particle spectra are obtained from an exact diagonalization by using a group-theoretical treatment. The electron-hole interaction is next introduced: Both the Coulomb (direct) and exchange terms are considered. The high-energy excitonic transitions are studied by computing the electric dipole transition probabilities between single-particle states, while the transition energies are obtained by taking into account the Coulomb interaction. The fine structure of the lowest excitonic states is analyzed by including the electron-hole exchange interaction and the wurtzite crystal-field terms in the exciton Hamiltonian. The latter is diagonalized in the single electron-hole pair excitation subspace of progressively increasing size until convergence. The peaks in the theoretical transition spectra are then used to deduce the resonant and nonresonant Stokes shifts, which are compared with their measured values in photoluminescence experiments. We find that the final results depend on the crystal-field term, the relative size of the surface and the degree of saturation of the dangling bonds. The results show a satisfactory agreement with the available experimental data.Comment: Revtex, 24 pages, 7 Postscript figure

Single cell analysis of kynurenine and System L amino acid transport in T cells

Acknowledgements We thank Cantrell group members for their critical discussion of the data, the Biological Resources unit, Sarah Thomson (for rLM work) and the Flow Cytometry facility (A. Whigham and R. Clarke) at the University of Dundee. This work was supported by the Wellcome Trust (Principal Research Fellowship to D.A.C. 097418/Z/11/Z and 205023/Z/16/Z, and Wellcome Trust Equipment Award 202950/Z/16/Z).Peer reviewedPublisher PD

Drying Shrinkage Mechanisms in Portland Cement Paste

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65426/1/j.1151-2916.1987.tb05002.x.pd

Selenoether oxytocin analogues have analgesic properties in a mouse model of chronic abdominal pain

Poor oral availability and susceptibility to reduction and protease degradation is a major hurdle in peptide drug development. However, drugable receptors in the gut present an attractive niche for peptide therapeutics. Here we demonstrate, in a mouse model of chronic abdominal pain, that oxytocin receptors are significantly upregulated in nociceptors innervating the colon. Correspondingly, we develop chemical strategies to engineer non-reducible and therefore more stable oxytocin analogues. Chemoselective selenide macrocyclization yields stabilized analogues equipotent to native oxytocin. Ultra-high-field nuclear magnetic resonance structural analysis of native oxytocin and the seleno-oxytocin derivatives reveals that oxytocin has a pre-organized structure in solution, in marked contrast to earlier X-ray crystallography studies. Finally, we show that these seleno-oxytocin analogues potently inhibit colonic nociceptors both in vitro and in vivo in mice with chronic visceral hypersensitivity. Our findings have potentially important implications for clinical use of oxytocin analogues and disulphide-rich peptides in general

cIAP1/2 Are Direct E3 Ligases Conjugating Diverse Types of Ubiquitin Chains to Receptor Interacting Proteins Kinases 1 to 4 (RIP1–4)

The RIP kinases have emerged as essential mediators of cellular stress that integrate both extracellular stimuli emanating from various cell-surface receptors and signals coming from intracellular pattern recognition receptors. The molecular mechanisms regulating the ability of the RIP proteins to transduce the stress signals remain poorly understood, but seem to rely only partially on their kinase activities. Recent studies on RIP1 and RIP2 have highlighted the importance of ubiquitination as a key process regulating their capacity to activate downstream signaling pathways. In this study, we found that XIAP, cIAP1 and cIAP2 not only directly bind to RIP1 and RIP2 but also to RIP3 and RIP4. We show that cIAP1 and cIAP2 are direct E3 ubiquitin ligases for all four RIP proteins and that cIAP1 is capable of conjugating the RIPs with diverse types of ubiquitin chains, including linear chains. Consistently, we show that repressing cIAP1/2 levels affects the activation of NF-κB that is dependent on RIP1, -2, -3 and -4. Finally, we identified Lys51 and Lys145 of RIP4 as two critical residues for cIAP1-mediated ubiquitination and NF-κB activation