Hydrophobic polymer monoliths as novel phase separators: Application in continuous liquid–liquid extraction systems

Hydrophobic macroporous polymer monoliths are shown to be interesting materials for the construction of “selective solvent gates”. With the appropriate surface chemistry and porous properties the monoliths can be made permeable only for apolar organic solvents and not for water. Different poly(butyl methacrylate-co-ethylene dimethacrylate) (BMA-EDMA) and poly(styrene-co-divinylbenzene) (PS-DVB) monoliths prepared with tailored chemistries and porosities were evaluated for this purpose. After extensive characterization, the PS-DVB monoliths were selected due to their higher hydrophobicity and their more suitable flow characteristics. BMA-EDMA monoliths are preferred for mid-polarity solvents such as ethyl acetate, for which they provide efficient separation from water. Breakthrough experiments confirmed that the pressures necessary to generate flow of organic solvents through PS-DVB monoliths were substantially lower than for water. A phase separator was constructed using the monoliths as the flow selector. This device was successfully coupled on-line with a chip-based continuous liquid–liquid-extraction (LLE) system with segmented flow. Efficient separation of different solvents was obtained across a wide range of flow rates (0.5–4.0 mL min⁻¹) and aqueous-to-organic flow ratios (β = 1–10). Good robustness and long life-time were also confirmed. The suitability of the device to perform simple, cheap, and reliable phase separation in a continuous LLE system prior to gas-chromatographic analysis was proven for some selected real-life applications.     

Myofibroblasts in the infarct area: concepts and challenges

Myofibroblasts are differentiated fibroblasts that hold a key role in wound healing and remodeling following myocardial infarction (MI). A large repertoire of stimuli, such as mechanical stretch, growth factors, cytokines, and vasoactive peptides, induces myofibroblast differentiation. Myofibroblasts are responsible for the production and deposition of collagen, leading to the establishment of a dense extracellular matrix that strengthens the infarcted tissue and minimizes dilatation of the infarct area. In addition, cells contributing to fibrosis act on sites distal from the infarct area and promote collagen deposition in noninfarcted tissue, thus contributing to adverse remodeling and consequently to the development of congestive heart failure (CHF). Current drugs that are used to treat post-MI CHF do influence fibroblasts and myofibroblasts; however, their therapeutic efficacy is far from being regarded as ideal. Novel therapeutic agents targeting (myo)fibroblasts are being developed to successfully prevent the cardiac remodeling of sites remote from the infarct area and therefore hinder the establishment of CHF. The purpose of this review article is to discuss the basic concepts of the myofibroblasts' actions in cardiac wound healing processes, factors that influence them, currently available pharmacological agents, and future challenges in this area.     

Enhancing the Photocurrent in Diketopyrrolopyrrole-Based Polymer Solar Cells via Energy Level Control

A series of diketopyrrolopyrrole (DPP)-based small band gap polymers has been designed and synthesized by Suzuki or Stille polymerization for use in polymer solar cells. The new polymers contain extended aromatic π-conjugated segments alternating with the DPP units and are designed to increase the free energy for charge generation to overcome current limitations in photocurrent generation of DPP-based polymers. In optimized solar cells with [6,6]phenyl-C(71)-butyric acid methyl ester ([70]PCBM) as acceptor, the new DPP-polymers provide significantly enhanced external and internal quantum efficiencies for conversion of photons into collected electrons. This provides short-circuit current densities in excess of 16 mA cm(-2), higher than obtained so far, with power conversion efficiencies of 5.8% in simulated solar light. We analyze external and internal photon to collected electron quantum efficiencies for the new polymers as a function of the photon energy loss, defined as the offset between optical band gap and open circuit voltage, and compare the results to those of some of the best DPP-based polymers solar cells reported in the literature. We find that for the best solar cells there is an empirical relation between quantum efficiency and photon energy loss that presently limits the power conversion efficiency in these devices.     

Imaging of ultrafast molecular elimination reactions

Ultrafast molecular elimination reactions are studied using the velocity map ion imaging technique in combination with femtosecond pump-probe laser excitation. A pump laser is used to initiate the dissociative reaction, and after a predetermined time delay a probe laser "interrogates" the molecular system. Ionic fragments are detected with a two-dimensional velocity map imaging detector providing detailed information about the energetic and vectorial properties of mass selected photofragments. In this paper we discuss the ultrafast elimination of molecular iodine, I(2), from IF(2)C-CF(2)I, where the iodine atoms originate from neighboring carbon atoms. By varying the femtosecond delay between pump and probe pulse, it is found that elimination of molecular iodine is a concerted process, although the two carbon-iodine bonds are not broken synchronously. Energetic considerations suggest that the crucial step in this fragmentation process is an electron transfer between the two iodine atoms in the parent molecule, which leads to Coulombic attraction and the creation of an ion-pair state in the molecular iodine fragment.     

A theoretical basis for parameter selection and instrument design in comprehensive size-exclusion chromatography x liquid chromatography

A novel approach for the selection of the operational parameters (linear velocity, column length) for a comprehensive 2D-LC system is discussed. Starting point for the calculations is a given second dimension ((2)D) separation and a desired peak capacity for the 2D system. Using the theory developed here the optimum settings for the first dimension ((1)D) column can be derived. Theory clearly indicates that the choice of the (1)D conditions is basically limited to just one set of column lengths and linear velocities. The new method is tested on a comprehensive two-dimensional liquid chromatography system which uses size-exclusion chromatography (SEC) followed by reversed phase liquid chromatography (RPLC). A novel LC/LC interface, using a six-port valve rather than storage loops, joins the two chromatographic dimensions. From a theoretical comparison of continuous low flow and stop-flow operation the latter method was found to be an attractive mode of interfacing. The common idea that stop-flow operation results in additional band broadening is shown to be incorrect. The new interface design operated in the stop-flow mode permits the use of conventional analytical diameter HPLC columns, 7.8mm for SEC and 4.6mm for RPLC. The reversed phase chromatography utilizes a monolithic C-18 modified silica column, which produces fast and efficient analyses. As test samples complex mixtures of peptides were analyzed.     

Tetraphenol-based diphosphite ligands: synthesis, characterization, and application in the rhodium-catalyzed hydroformylation of octenes

A new class of diphosphites is described, based on a tetraphenol backbone. Ligands TP1-TP5 were synthesized and fully characterized and their application in the hydroformylation of octenes was investigated. Ligand TP3, bearing a 1-naphthoxy substituent on the phosphorus, shows the highest regioselectivity toward the linear aldehyde.     

The n‐ordered graphs: A new graph class

For a positive integer n, we introduce the new graph class of n‐ordered graphs, which generalize partial n‐trees. Several characterizations are given for the finite n‐ordered graphs, including one via a combinatorial game. We introduce new countably infinite graphs R⁽ⁿ⁾, which we name the infinite random n‐ordered graphs. The graphs R⁽ⁿ⁾ play a crucial role in the theory of n‐ordered graphs, and are inspired by recent research on the web graph and the infinite random graph. We characterize R⁽ⁿ⁾ as a limit of a random process, and via an adjacency property and a certain folding operation. We prove that the induced subgraphs of R⁽ⁿ⁾ are exactly the countable n‐ordered graphs. We show that all countable groups embed in the automorphism group of R⁽ⁿ⁾. © 2008 Wiley Periodicals, Inc. J Graph Theory 60: 204–218, 2009     

Parameter selection for peak alignment in chromatographic sample profiling: objective quality indicators and use of control samples

In chromatographic profiling applications, peak alignment is often essential as most chromatographic systems exhibit small peak shifts over time. When using currently available alignment algorithms, there are several parameters that determine the outcome of the alignment process. Selecting the optimum set of parameters, however, is not straightforward, and the quality of an alignment result is at least partly determined by subjective decisions. Here, we demonstrate a new strategy to objectively determine the quality of an alignment result. This strategy makes use of a set of control samples that are analysed both spiked and non-spiked. With this set, not only the system and the method can be checked but also the quality of the peak alignment can be evaluated. The developed strategy was tested on a representative metabolomics data set using three software packages, namely Markerlynx™, MZmine and MetAlign. The results indicate that the method was able to assess and define the quality of an alignment process without any subjective interference of the analyst, making the method a valuable contribution to the data handling process of chromatography-based metabolomics data.