A robust comparison of dynamical scenarios in a glass-forming liquid

We use Bayesian inference methods to provide fresh insights into the sub-nanosecond dynamics of glycerol, a prototypical glass-forming liquid. To this end, quasielastic neutron scattering data as a function of temperature have been analyzed using a minimal set of underlying physical assumptions. On the basis of this analysis, we establish the unambiguous presence of three distinct dynamical processes in glycerol, namely, translational diffusion of the molecular centre of mass and two additional localized and temperature-independent modes. The neutron data also provide access to the characteristic length scales associated with these motions in a model-independent manner, from which we conclude that the faster (slower) localized motions probe longer (shorter) length scales. Careful Bayesian analysis of the entire scattering law favors a heterogeneous scenario for the microscopic dynamics of glycerol, where molecules undergo either the faster and longer or the slower and shorter localized motions.Peer ReviewedPostprint (author's final draft

Dynamics of bound states of dihydrogen at Cu(I) and Cu(II) species coordinated near one and two zeolite framework aluminium atoms: A combined sorption, INS, IR and DFT study

Abstract Ambient conditions sorption isotherms of dihydrogen in a series of various levels of Cu-exchanged ZSM-5 zeolites, with two different Si/Al ratios, namely 11.5 and 25, show the presence of different amount of Cu centres able to strongly bind H2. Although the isosteric heats of adsorption derived from these isotherms are rather similar, of the order of 30 kJ/mol H2, Inelastic Neutron Scattering (INS) of adsorbed dihydrogen and Fourier-Transformed Infra-Red (FTIR) spectroscopy measurements of adsorbed CO and NO reveal that copper is encountered in two oxidation states. At least two types of Cu(I) ions are clearly detected as well as some heterogeneity of the Cu(II) species. The number of these Cu species is different in the two investigated ZSM-5 materials and depends on the Cu exchange level. With the aid of DFT model cluster calculations we find that under different coordination environments, determined by the Al distribution, both mono- and divalent Cu ions could bind H2 with a different strength. Unprecedentedly, we found that Cu-ions compensating two Al atoms, i.e. formally Cu(II) species, relatively far apart from each other, may behave very similarly to the monovalent Cu-species or alternatively viewed – as Cu(I) species that compensate for two framework Al-atoms. Such Cu-species also form stable η2 dihydrogen complexes

Evolution of Optoelectronic and Texture Properties

We show a simple room temperature surface functionalization approach using iodine vapour to control a surface phase transition from cubic silver (Ag) of thin films into wurtzite silver-iodid (β-AgI) films. A combination of surface characterization techniques (optical, electronical and structural characterization) reveal distinct physical properties of the new surface phase. We discuss the AgI thin film formation dynamics and related transformation of physical properties by determining the work-function, dielectric constant and pyroelectric behavior together with morphological and structural thin film properties such as layer thickness, grain structure and texture formation. Notable results are: (i) a remarkable increase of the work- function (by 0.9 eV) of the Ag thin layer after short a iodine exposure time (≤60 s), with simultaneous increase of the thin film transparency (by two orders of magnitude), (ii) pinning of the Fermi level at the valance band maximum upon iodine functionalization, (iii) 84% of all crystallites grain were aligned as a result of the evolution of an internal electric field. Realizing a nano-scale layer stack composed of a dielectric AgI layer on top of a metallic thin Ag layer with such a simple method has some technological implications e.g. to realize optical elements such as planar optical waveguides

Rapid fabrication and interface structure of highly faceted epitaxial Ni-Au solid solution nanoparticles on sapphire

Supersaturated Ni-Au solid solution particles were synthesized by rapid solid-state dewetting of bilayer thin films deposited onto c-plane sapphire single-crystals. Rapid thermal annealing above the miscibility gap of the Ni-Au system followed by quenching to room temperature resulted in textured and faceted submicron-sized particles as a function of alloying content in the range of 0-28 at% Au. Morphologically, the observed kinetic crystal shapes are confined by close-packed planes; in addition, high-index facets are identified as a function of alloying content by TEM cross-sectioning and equilibrium crystal shape simulations. All samples exhibit a distinct out-of-plane as well as in-plane texture along densely packed directions. Lattice parameters extracted from independent orthogonal X-ray and electron diffraction techniques prove the formation of a solid solution without tetragonal distortion imposed by the sapphire substrate. At the particle-substrate interface of highly alloyed particles segregation of Au atoms as well as dislocations in stand-off position are found. These observations are in-line with a semi-coherent interface, where Au segregation is triggered by the reduction of the overall strain energy due to: (i) a lower shear modulus on the particle side of the interface, (ii) the shifting of misfit dislocations in stand-off position further away from the stiffer substrate and (iii) a reduction of intrinsic misfit dislocation strain energy on the tensile side. In addition, the mechanical properties of pure and alloyed particles were characterized by in situ compression experiments in the SEM. Typical force-displacement data of defect-free single-crystals were obtained, reaching the theoretical strength of Ni for particles smaller than 400 nm. Alloying changes the mechanical response from an intermittent and discrete plastic flow behavior into a homogeneous deformation regime at large compressive strain

Kinky DNA in solution: Small-angle-scattering study of a nucleosome positioning sequence

DNA is a flexible molecule, but the degree of its flexibility is subject to debate. The commonly-accepted persistence length of lp ≈ 500Å is inconsistent with recent studies on short-chain DNA that show much greater flexibility but do not probe its origin. We have performed x-ray and neutron small-angle scattering on a short DNA sequence containing a strong nucleosome positioning element and analyzed the results using a modified Kratky-Porod model to determine possible conformations. Our results support a hypothesis from Crick and Klug in 1975 that some DNA sequences in solution can have sharp kinks, potentially resolving the discrepancy. Our conclusions are supported by measurements on a radiation-damaged sample, where single-strand breaks lead to increased flexibility and by an analysis of data from another sequence, which does not have kinks, but where our method can detect a locally enhanced flexibility due to an AT domain.Spanish Ministry of Economy, Industry and Competitiveness (BES-2013-065453, EEBB-I-2015-09973, FIS2012-38827). S.C.L. and UC-154 are grateful for the support of Junta de Castilla y Leon (Spain) Nanofibersafe BU079U16. D.A. acknowledges funding from the Agence Nationale de la Recherche through ANR-12-BSV5-0017-01 “Chrome” and ANR-17-CE11-0019-03 “Chrom3D” grants. N.T. acknowledges support by the project Advanced Materials and Devices (MIS 5002409, Competitiveness, Entrepreneurship and Innovation, NSRF 2014-2020) cofinanced by Greece and the European Regional Development Fund

The role of connectivity in significant bandgap narrowing for fused-pyrene based non-fullerene acceptors toward high-efficiency organic solar cells

Great attention has been paid to developing low bandgap non-fullerene acceptors (NFAs) for matching wide bandgap donor polymers to increase the photocurrent and therefore the power conversion efficiencies (PCEs) of NFA organic solar cells, while pyrene-core based acceptor-donor-acceptor (A-D-A) NFAs have been mainly reported via the 2,9-position connection due to their bisthieno[3′,2′-b']thienyl[a,h]pyrene fused via a five-membered ring bridge at the ortho-position of pyrene as the representative one named FPIC5, which has prohibited further narrowing their energy gap. Herein, an acceptor FPIC6 was exploited by creating the 1,8-position connection through fusing as bisthieno[3′,2′-b′]thienyl[f-g,m-n]pyrene linked at the bay-position via a six-membered bridge, with enhanced push-pull characteristics within such A-D-A structure. As a structural isomer of FPIC5, FPIC6 exhibited a much lower bandgap of 1.42 eV (1.63 eV for FPIC5). Therefore, the photocurrent and PCE of PTB7-Th:FPIC6 cells were improved to 21.50 mA cm-2 and 11.55%, respectively, due to the balanced mobilities, better photoluminescence quenching efficiency and optimized morphology, which are both ∼40% better than those of PTB7-Th:FPIC5 cells. Our results clearly proved that a pyrene fused core with 1,8-position connection with electron-withdrawing end groups instead of 2,9-position connection is an efficient molecular design strategy to narrow the optical bandgap and improve the photovoltaic performance of NFA based OSCs

Ring1b-dependent epigenetic remodelling is an essential prerequisite for pancreatic carcinogenesis

BACKGROUND AND AIMS Besides well-defined genetic alterations, the dedifferentiation of mature acinar cells is an important prerequisite for pancreatic carcinogenesis. Acinar-specific genes controlling cell homeostasis are extensively downregulated during cancer development; however, the underlying mechanisms are poorly understood. Now, we devised a novel in vitro strategy to determine genome-wide dynamics in the epigenetic landscape in pancreatic carcinogenesis. DESIGN With our in vitro carcinogenic sequence, we performed global gene expression analysis and ChIP sequencing for the histone modifications H3K4me3, H3K27me3 and H2AK119ub. Followed by a comprehensive bioinformatic approach, we captured gene clusters with extensive epigenetic and transcriptional remodelling. Relevance of Ring1b-catalysed H2AK119ub in acinar cell reprogramming was studied in an inducible Ring1b knockout mouse model. CRISPR/Cas9-mediated Ring1b ablation as well as drug-induced Ring1b inhibition were functionally characterised in pancreatic cancer cells. RESULTS The epigenome is vigorously modified during pancreatic carcinogenesis, defining cellular identity. Particularly, regulatory acinar cell transcription factors are epigenetically silenced by the Ring1b-catalysed histone modification H2AK119ub in acinar-to-ductal metaplasia and pancreatic cancer cells. Ring1b knockout mice showed greatly impaired acinar cell dedifferentiation and pancreatic tumour formation due to a retained expression of acinar differentiation genes. Depletion or drug-induced inhibition of Ring1b promoted tumour cell reprogramming towards a less aggressive phenotype. CONCLUSIONS Our data provide substantial evidence that the epigenetic silencing of acinar cell fate genes is a mandatory event in the development and progression of pancreatic cancer. Targeting the epigenetic repressor Ring1b could offer new therapeutic options