Evidence of environmental strains on charge injection in silole based organic light emitting diodes

Using d. functional theory (DFT) computations, the authors demonstrated a substantial skeletal relaxation when the structure of 2,5-bis-[4-anthracene-9-yl-phenyl]-1,1-dimethyl-3,4-diphenyl-silole (BAS) is optimized in the gas-phase comparing with the mol. structure detd. from monocrystal x-ray diffraction. The origin of such a relaxation is explained by a strong environmental strains induced by the presence of anthracene entities. Also, the estn. of the frontier orbital levels showed that this structural relaxation affects mainly the LUMO that is lowered of 190 meV in the gas phase. To check if these theor. findings would be confirmed for thin films of BAS, the authors turned to UV photoemission spectroscopy and/or inverse photoemission spectroscopy and electrooptical measurements. The study of the c.d. or voltage and luminance or voltage characteristics of an ITO/PEDOT/BAS/Au device clearly demonstrated a very unusual temp.-dependent behavior. Using a thermally assisted tunnel transfer model, this behavior likely originated from the variation of the electronic affinity of the silole deriv. with the temp. The thermal agitation relaxes the mol. strains in thin films as it is shown when passing from the cryst. to the gas phase. The relaxation of the intramol. thus induces an increase of the electronic affinity and, as a consequence, the more efficient electron injection in org. light-emitting diodes

Bismuth coordination networks containing deferiprone: synthesis, characterisation, stability and antibacterial activity

A series of bismuth–dicarboxylate–deferiprone coordination networks have been prepared and structurally characterised. The new compounds have been demonstrated to release the iron overload drug deferiprone on treatment with PBS and have also been shown to have antibacterial activity against H. pylori

Aqua­(2,2′-bipyridine-κ2 N,N′)bis­(thio­phene-2-carboxyl­ato-κO)copper(II)

In the title complex, [Cu(C5H3O2S)2(C10H8N2)(H2O)], the CuII atom is in a distorted square-pyramidal environment, with an Addison τ parameter of 0.07. The coordination geometry is defined by two nitro­gen donors from the 2,2′-bipyridine ligand, two O atoms from two monodentate thio­phene-2-carboxyl­ate ligands and one O atom from the aqua ligand. The latter occupies the elongated apical position. This is different from the related structure of aqua­(1,10-phenanthroline)bis­(thio­phene-2-carboxyl­ato)copper(II) where a carboxyl­ate O atom is in the apical position [Feng et al. (2005 ▶). Z. Kristallogr. New Cryst. Struct. 220, 429–430]. The uncoordinated carboxyl­ate O atoms form intra- and inter­molecular hydrogen bonds to the aqua ligand. Two neighbouring 2,2′-bipyridine ligands form a π-stack, with a centroid–centroid distance of 3.683 (2) Å

Supramolecular assemblies involving metal organic ring interactions: Heterometallic Cu(II)-Ln(III) two dimensional coordination polymers

Three isostructural two-dimensional coordination polymers of the general formula [Ln2(CuL)3(H2O)9]$5.5H2O, where Ln is La (1), Nd (2), and Gd (3), have been synthesized and isolated from aqueous solutions and their single-crystal structures determined by X-ray diffraction. The supramolecular interaction between the non-aromatic metallorings plays an important role in stabilizing the structure of these compounds. The thermal stability, reversible solvent uptake, electronic properties and magnetic studies of these compounds are also reported

Incorporation by coordination and release of the iron chelator drug deferiprone from zinc-based metal–organic frameworks

A series of new zinc-based metal–organic framework materials has been prepared in which deferiprone is incorporated as a chelating ligand on infinite or tri-zinc secondary building units following deprotonation. Deferiprone is immediately released from the MOFs on treatments with 1 N hydrochloric acid or buffer, but slow release is observed in ethanoic acid

Philosophy and Science in Leibniz

This paper explores the question of Leibniz’s contribution to the rise of modern ‘science’. To be sure, it is now generally agreed that the modern category of ‘science’ did not exist in the early modern period. At the same time, this period witnessed a very important stage in the process from which modern science eventually emerged. My discussion will be aimed at uncovering the new enterprise, and the new distinctions which were taking shape in the early modern period under the banner of the old Aristotelian terminology. I will argue that Leibniz begins to theorize a distinction between physics and metaphysics that tracks our distinction between the autonomous enterprise of science in its modern meaning, and the enterprise of philosophy. I will try to show that, for Leibniz, physics proper is the study of natural phenomena in mathematical and mechanical terms without recourse for its explanations to metaphysical notions. This autonomy, however, does not imply for Leibniz that physics can say on its own all that there is to be said about the natural world. Quite the opposite. Leibniz inherits from the Aristotelian tradition the view that physics needs metaphysical roots or a metaphysical grounding. For Leibniz, what is ultimately real is reached by metaphysics, not by physics. This is, in my view, Leibniz’s chief insight: the new mathematical physics is an autonomous enterprise which offers its own kind of explanations but does not exhaust what can (and should) be said about the natural world

T-Cell Exhaustion in HIV-1/Hepatitis C Virus Coinfection Is Reduced After Successful Treatment of Chronic Hepatitis C.

BACKGROUND T-cell responses during chronic viral infections become exhausted, which is reflected by upregulation of inhibitory receptors (iRs) and increased interleukin 10 (IL-10). We assessed 2 iRs-PD-1 (programmed cell death protein 1) and Tim-3 (T-cell immunoglobulin and mucin domain-containing protein 3)-and IL-10 mRNAs in peripheral blood mononuclear cells (PBMCs) and their soluble analogs (sPD-1, sTim-3, and IL-10) in plasma in chronic HIV-1/hepatitis C virus (HCV) coinfection and explored the effect of HCV treatment on these markers. We also aimed to establish whether iR expression may be determined by the HCV CD8+ T-cell immunodominant epitope sequence. METHODS Plasma and PBMCs from 31 persons with chronic HIV-1/HCV coinfection from the Swiss HIV Cohort Study were collected before and after HCV treatment. As controls, 45 persons who were HIV-1 negative with chronic HCV infection were recruited. Exhaustion markers were assessed by enzyme-linked immunosorbent assay in plasma and by quantitative reverse transcription polymerase chain reaction in PBMCs. Analysis of an HCV epitope sequence was conducted by next-generation sequencing: HLA-A*02-restricted NS31073-1081 and NS31406-1415 and HLA-A*01-restricted NS31436-1444. RESULTS The study revealed higher plasma sPD-1 (P = .0235) and IL-10 (P = .002) levels and higher IL-10 mRNA in PBMCs (P = .0149) in HIV-1/HCV coinfection. A decrease in plasma sPD-1 (P = .0006), sTim-3 (P = .0136), and IL-10 (P = .0003) and Tim-3 mRNA in PBMCs (P = .0210) was observed following successful HCV treatment. Infection with the HLA-A*01-restricted NS31436-1444 ATDALMTGY prototype variant was related to higher sTim-3 levels than infection with the ATDALMTGF escape variant (P = .0326). CONCLUSIONS The results underscore the synergistic effect of coinfection on expression of exhaustion markers, their reduction following successful HCV treatment and imply that iR levels may operate on an epitope-specific manner

T-Cell Exhaustion in HIV-1/Hepatitis C Virus Coinfection Is Reduced After Successful Treatment of Chronic Hepatitis C

BACKGROUND T-cell responses during chronic viral infections become exhausted, which is reflected by upregulation of inhibitory receptors (iRs) and increased interleukin 10 (IL-10). We assessed 2 iRs-PD-1 (programmed cell death protein 1) and Tim-3 (T-cell immunoglobulin and mucin domain-containing protein 3)-and IL-10 mRNAs in peripheral blood mononuclear cells (PBMCs) and their soluble analogs (sPD-1, sTim-3, and IL-10) in plasma in chronic HIV-1/hepatitis C virus (HCV) coinfection and explored the effect of HCV treatment on these markers. We also aimed to establish whether iR expression may be determined by the HCV CD8$^{+}$ T-cell immunodominant epitope sequence. METHODS Plasma and PBMCs from 31 persons with chronic HIV-1/HCV coinfection from the Swiss HIV Cohort Study were collected before and after HCV treatment. As controls, 45 persons who were HIV-1 negative with chronic HCV infection were recruited. Exhaustion markers were assessed by enzyme-linked immunosorbent assay in plasma and by quantitative reverse transcription polymerase chain reaction in PBMCs. Analysis of an HCV epitope sequence was conducted by next-generation sequencing: HLA-A*02-restricted NS3$_{1073-1081}$ and NS3$_{1406-1415}$ and HLA-A*01-restricted NS3$_{1436-1444}$. RESULTS The study revealed higher plasma sPD-1 (P = .0235) and IL-10 (P = .002) levels and higher IL-10 mRNA in PBMCs (P = .0149) in HIV-1/HCV coinfection. A decrease in plasma sPD-1 (P = .0006), sTim-3 (P = .0136), and IL-10 (P = .0003) and Tim-3 mRNA in PBMCs (P = .0210) was observed following successful HCV treatment. Infection with the HLA-A*01-restricted NS3$_{1436-1444}$ ATDALMTGY prototype variant was related to higher sTim-3 levels than infection with the ATDALMTGF escape variant (P = .0326). CONCLUSIONS The results underscore the synergistic effect of coinfection on expression of exhaustion markers, their reduction following successful HCV treatment and imply that iR levels may operate on an epitope-specific manner