Experimental and Theoretical Investigation of Vibrational Spectra of Coordination Polymers Based on TCE‐TTF

The room‐temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7‐tetrakis(2‐cyanoethylthio)‐tetrathiafulvalene (TCE‐TTF) with paramagnetic (Co^II, Mn^II) and diamagnetic (Zn^II, Cd^II) ions, together with BF₄^? or ClO₄^? anions are reported. Infrared and Raman‐active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE‐TTF using density functional theory (DFT) methods. It is confirmed that the TCE‐TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C?C stretching vibrations of TCE‐TTF are analyzed assuming the occurrence of electron–molecular vibration coupling (EMV). The presence of the antisymmetric C?C dimeric mode provides evidence that charge transfer takes place between TCE‐TTF molecules belonging to neighboring polymeric networks.     

Contribution from a hole-conducting dye to the photocurrent in solid-state dye-sensitized solar cells

The hole transporting medium in solid-state dye-sensitized solar cells can be utilized to harvest sunlight. Herein we demonstrate that a triphenylamine-based dye, used as hole-transporting medium, contributes to the photocurrent in a squaraine-sensitized solid-state dye-sensitized solar cell. Steady-state photoluminescence measurements have been used to distinguish between electron transfer and energy transfer processes leading to energy conversion upon light absorption in the hole-transporting dye.     

Pressure-amorphized cubic structure II clathrate hydrate: crystallization in slow motion

A range of techniques has so far been employed for producing amorphous aqueous solutions. In case of aqueous tetrahydrofuran (THF) this comprises hyperquenching of liquid droplets, vapour co-deposition and pressure-induced amorphization of the crystalline cubic structure II clathrate. All of these samples are thermally labile and crystallize at temperatures above 110 K. We here outline a variant of the pressure-amorphization protocol developed by Suzuki [Phys. Rev. B, 2004, 70, 172108], which results in a highly crystallization resistant amorphous THF hydrate. The hydrate produced according to our protocol (annealing to 180 K at 1.8 GPa rather than to 150 K at 1.5 GPa) does not transform to the cubic structure II THF clathrate even at 150 K. We track the reason for this higher stability to the presence of crystalline remnants when following the Suzuki protocol, which are removed when using our protocol involving higher pressures and an annealing step. These crystalline remnants later serve as crystallization seeds lowering the thermal stability of the amorphous sample. Our protocol thus makes a purely amorphous THF hydrate available to the research community. We use powder X-ray diffraction to study the process of nucleation and slow crystal growth in the temperature range 160-200 K and find that the local cage structure and periodicity of the fully crystalline hydrate develops even at the earliest stages of crystallization, when the "clathrate crystal" has a size of about two unit cells.     

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ?(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous.     

Gas-phase binding energies for non-covalent Aβ-40 peptide/small molecule complexes from CID mass spectrometry and RRKM theory

The gas-phase binding of small molecules to the Amyloid β-40 peptide generated by electrospray ionization has been explored with collision-induced dissociation mass spectrometry and kinetic rate theory. This study discusses a simple procedure used to theoretically model the experimental breakdown diagrams for the Aβ-40 peptide complexed with a series of aminosulfonate small molecules, namely homotaurine, 3-cyclohexylamino-2-hydroxy-1-propanesulfonic acid (CAPSO), 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)propane-1-sulfonic acid, 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)butane-1-sulfonic acid, and 3-(cyclohexylamino)propane-1-sulfonic acid. An alternative procedure employing an extrapolation procedure for k(E) is also discussed.     

Tumour cell identification by means of Raman spectroscopy in combination with optical traps and microfluidic environments

Raman spectroscopy has been recognized to be a powerful tool for label-free discrimination of cells. Sampling methods are under development to utilize the unique capabilities to identify cells in body fluids such as saliva, urine or blood. The current study applied optical traps in combination with Raman spectroscopy to acquire spectra of single cells in microfluidic glass channels. Optical traps were realized by two 1070 nm single mode fibre lasers. Microflows were controlled by a syringe pump system. A novel microfluidic glass chip was designed to inject single cells, modify the flow speed, accommodate the laser fibres and sort cells after Raman based identification. Whereas the integrated microchip setup used 514 nm for excitation of Raman spectra, a quartz capillary setup excited spectra with 785 nm laser wavelength. Classification models were trained using linear discriminant analysis to differentiate erythrocytes, leukocytes, acute myeloid leukaemia cells (OCI-AML3), and breast tumour cells BT-20 and MCF-7 with accuracies that are comparable with previous Raman experiments of dried cells and fixed cells in a Petri dish. Implementation into microfluidic environments enables a high degree of automation that is required to improve the throughput of the approach for Raman activated cell sorting.     

Repository-Scale Modeling of the Long-Term Hydraulic Perturbation Induced by Gas and Heat Generation in a Geological Repository for High-and Intermediate-Level Radioactive Waste: Methodology and Example of Application

The current design of a deep geological repository for high- and intermediate-level radioactive waste in France consists of a complex system of different underground structures (ANDRA, Dossier 2005 Argile, les recherches de l’Andra sur le stockage géologique des déchets radioactifs à haute activité et à vie longue, collection les Rapports. Chatenay-Malabry, France, 2005). For a comprehensive understanding of the long-term hydraulic evolution of the entire repository, numerical non-isothermal two-phase flow and transport simulation, taking into consideration the generation, accumulation, and release of hydrogen gas and decay heat, are compulsory. However, a detailed numerical model of the entire repository system would require a tremendous computational effort and pose a laborious task with respect to the operation of the model. To handle these difficulties, we have developed an efficient method for the numerical modeling of a complete repository system and its geologic environment. The method consists of the following steps: (i) subdivision of the repository plane into a large number of “sectors” based on the position of hydraulic seals and on other geometrical considerations, (ii) exploitation of existing symmetries (inside or between sectors), (iii) adoption of the “multiplying concept”, and (iv) connection of the individual sectors at the drift interfaces to form the entire repository model. Each sector is modeled as a three-dimensional (3D) block, and the entire model is computed with TOUGH2-MP. The method allows for a massive reduction in overall finite-volume elements and, at the same time, provides an adequate representation of the small-sized structures in the repository. The main characteristics of the method and its application to an entire deep geological repository system in a clay host rock are presented.     

The CRT is the scaling limit of unordered binary trees

We prove that a uniform, rooted unordered binary tree (also known as rooted, binary Pólya tree) with n leaves has the Brownian continuum random tree as its scaling limit for the Gromov‐Hausdorff topology. The limit is thus, up to a constant factor, the same as that of uniform plane trees or labeled trees. Our analysis rests on a combinatorial and probabilistic study of appropriate trimming procedures of trees. © 2011 Wiley Periodicals, Inc. Random Struct. Alg., 38, 467–501, 2011     

Radial Solutions of Neumann Problem for Periodic Perturbations of the Mean Extrinsic Curvature Operator

In this paper we survey some recent results on the existence and multiplicity of radial solutions for Neumann problems in a ball and in an annular domain, associated to pendulum-like perturbations of the mean extrinsic curvature operator in Minkowski space. Our approach relies on the Leray-Schauder degree, upper and lower solutions, and critical point theory.     

DMulti-MADS: mesh adaptive direct multisearch for bound-constrained blackbox multiobjective optimization

Computational Optimization and Applications - The context of this research is multiobjective optimization where conflicting objectives are present. In this work, these objectives are only available...