Accelerating research into bio-based FDCA-polyesters by using small scale parallel film reactors

High Throughput experimentation has been well established as a tool in early stage catalyst development and catalyst and process scale-up today. One of the more challenging areas of catalytic research is polymer catalysis. The main difference with most non-polymer catalytic conversions is the fact that the product is not a well defined molecule and the catalytic performance cannot be easily expressed only in terms of catalyst activity and selectivity. In polymerization reactions, polymer chains are formed that can have various lengths (resulting in a molecular weight distribution rather than a defined molecular weight), that can have different compositions (when random or block co-polymers are produced), that can have cross-linking (often significantly affecting physical properties), that can have different endgroups (often affecting subsequent processing steps) and several other variations. In addition, for polyolefins, mass and heat transfer, oxygen and moisture sensitivity, stereoregularity and many other intrinsic features make relevant high throughput screening in this field an incredible challenge. For polycondensation reactions performed in the melt often the viscosity becomes already high at modest molecular weights, which greatly influences mass transfer of the condensation product (often water or methanol). When reactions become mass transfer limited, catalyst performance comparison is often no longer relevant. This however does not mean that relevant experiments for these application areas cannot be performed on small scale. Relevant catalyst screening experiments for polycondensation reactions can be performed in very efficient small scale parallel equipment. Both transesterification and polycondensation as well as post condensation through solid-stating in parallel equipment have been developed. Next to polymer synthesis, polymer characterization also needs to be accelerated without making concessions to quality in order to draw relevant conclusions.     

Automated Determination of Captopril by Flow and Sequential Injection Analysis: A Review

The present study intends to present a review of automated methods for the determination of Captopril—an angiotensin converting enzyme (ACE) inhibitor—using flow or sequential injection analysis. The review covers a range of more than fifteen years of published research on this topic (1993–today). The methods are classified according to the detection systems in three categories, namely spectrophotometric, chemiluminescence, and electroanalytical. The principles and main analytical figures of merit of the reported studies are presented and discussed.     

The growth of membrane technology

Not all journal articles come out of the same mold. This one is a hybrid. It has some of the elements of a review. But any comprehensive review of the membrane technology field written today would have to contain even more references than this one does. It is also partly an overview, giving my opinions of what, among all the work done in this field over the past two centuries or so, is most relevant: what were the seminal works that led to the present state of development of membrane technology. Further, in places this article is a bit tutorial, and for this I ask the informed reader's indelgence. Finally, it is a somewhat personalized story, as the interested reader who suffers through all of the References and Notes will discover.     

The potential of proton exchange membrane–based electrolysis technology

Hydrogen is an important chemical feedstock for many industrial applications, and today, more than 95% of this feedstock is generated from fossil fuel sources such as reforming of natural gas. In addition, the production of hydrogen from fossil fuels represents most carbon dioxide emissions from large chemical processes such as ammonia generation. Renewable sources of hydrogen such as hydrogen from water electrolysis need to be driven to similar production costs as methane reforming to address global greenhouse gas emission concerns. Water electrolysis has begun to show scalability to relevant capacities to address this need, but materials and manufacturing advancements need to be made to meet the cost targets. This article describes specific needs for one pathway based on proton exchange membrane electrolysis technology.     

The Resist Technique—A Chemical Contribution to Electronics

Besides its technical meaning, the word “electronics” signifies another industrial revolution. The driving force behind this development is the very rapid progress in the field of integrated semiconductor circuits. An ever-increasing number of structures of ever-decreasing size must be accommodated on the same surface of the semiconductor crystal. This trend towards miniaturization embraces not only the integrated circuit but also its mounting panel, the printed circuit board; integrated circuits with 65 536 storage spaces, i.e. more than 100 000 individual functions, on a semiconductor die of less than 1 cm² are already standard today in industry. This micro-world, the potential of which can hardly be fully appreciated even today, has a direct appeal to all those of scientific inclination. However, the role of chemistry in the creation of this world becomes clear only on closer examination of the manufacturing processes: no mechanical tool is fine enough and no machine is sufficiently precise and rapid to work out complicated structures in the micron range with the required perfection. Chemistry first made possible the mass production of electronic components and consequently their widespread use today, and it is chemistry which will also play a decisive role in the future. Whether in the field of photoresists for the production of printed circuit boards with conductor widths of less than 100 μm, or in overcoming the 1 μm barrier in the manufacture of semiconductors using electron beam- and X-ray-resists, photochemistry, radiation chemistry, and polymer chemistry will have to develop new manufacturing processes and provide industrially utilizable materials.     

Hyphenated analytical techniques for multidimensional characterisation of submicron particles: a review

The stakes concerning the characterisation of particles ranged in the size from 1 to 1000 nm, namely submicron particles, are today more and more important. Because of the variety of particles even inside a given sample in terms of dimension, mass, charge or chemical composition a characterisation as complete as possible is needed. The possibility of obtaining a multidimensional information by relevant analytical methods is then of the greatest interest. One very interesting strategy consists in using hyphenated techniques, which are intrinsically capable to provide rapidly and accurately such information. This paper summarises the different hyphenated techniques that can be used to characterise submicron particles and is focussed on their main applications to illustrate their current and potential uses. In order to have a relevant overview various on-line separation techniques are considered in a comparative way. In the same way various on-line detectors are then presented. Finally the concepts of multidetection and multidimensional analysis are discussed and their interest showed through different typical examples of hyphenated techniques illustrating submicron particle characterisation in fields of applications such as environmental and nanomaterial sciences.     

Mechanistic Investigations into the Application of Sulfoxides in Carbohydrate Synthesis

The utility of sulfoxides in a diverse range of transformations in the field of carbohydrate chemistry has seen rapid growth since the first introduction of a sulfoxide as a glycosyl donor in 1989. Sulfoxides have since developed into more than just anomeric leaving groups, and today have multiple roles in glycosylation reactions. These include as activators for thioglycosides, hemiacetals, and glycals, and as precursors to glycosyl triflates, which are essential for stereoselective β‐mannoside synthesis, and bicyclic sulfonium ions that facilitate the stereoselective synthesis of α‐glycosides. In this review we highlight the mechanistic investigations undertaken in this area, often outlining strategies employed to differentiate between multiple proposed reaction pathways, and how the conclusions of these investigations have and continue to inform upon the development of more efficient transformations in sulfoxide‐based carbohydrate synthesis.     

Formation of Calcareous Deposit during CathodicProtection and Its Properties

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Developments in external quality assessment for clinical microbiology laboratories

There has been considerable development in external quality assessment programs for clinical microbiology laboratories. Over the last 5 years samples have progressively become more clinically realistic and relevant. Programs are tending to produce more samples that look and act like real samples. As programs change to a broader range of challenge targets, the observed rate of errors is substantially greater for pre-analytic and post-analytic challenges than with analytic phase challenges. Rather than focusing only on analytic phase procedures, schemes should target to a greater extent pre-analytic and post-analytic aspects of the laboratory cycle.Fourth EURACHEM/CITAC/EQUALM International Workshop on Proficiency Testing in Analytical Chemistry, Microbiology and Laboratory Medicine, UK, February 2003.     

Analysis and prediction of RNA-binding residues using sequence, evolutionary conservation, and predicted secondary structure and solvent accessibility

Identification and prediction of RNA-binding residues (RBRs) provides valuable insights into the mechanisms of protein-RNA interactions. We analyzed the contributions of a wide range of factors including amino acid sequence, evolutionary conservation, secondary structure and solvent accessibility, to the prediction/characterization of RBRs. Five feature sets were designed and feature selection was performed to find and investigate relevant features. We demonstrate that (1) interactions with positively charged amino acids Arg and Lys are preferred by the egatively charged nucleotides; (2) Gly provides flexibility for the RNA binding sites; (3) Glu with negatively charged side chain and several hydrophobic residues such as Leu, Val, Ala and Phe are disfavored in the RNA-binding sites; (4) coil residues, especially in long segments, are more flexible (than other secondary structures) and more likely to interact with RNA; (5) helical residues are more rigid and consequently they are less likely to bind RNA; and (6) residues partially exposed to the solvent are more likely to form RNA-binding sites. We introduce a novel sequence-based predictor of RBRs, RBRpred, which utilizes the selected features. RBRpred is comprehensively tested on three datasets with varied atom distance cutoffs by performing both five-fold cross validation and jackknife tests and achieves Matthew's correlation coefficient (MCC) of 0.51, 0.48 and 0.42, respectively. The quality is comparable to or better than that for state-of-the-art predictors that apply the distancebased cutoff definition. We show that the most important factor for RBRs prediction is evolutionary conservation, followed by the amino acid sequence, predicted secondary structure and predicted solvent accessibility. We also investigate the impact of using native vs. predicted secondary structure and solvent accessibility. The predictions are sufficient for the RBR prediction and the knowledge of the actual solvent accessibility helps in predictions for lower distance cutoffs.     

Colloidal interactions mediated by end-adsorbing polymer-like micelles

We derive a statistical mechanical model for colloidal interactions mediated by polymer-like micelles (PLMs) that adsorb at the colloid surface. The model considers the end-adsorption and reversible scission of ideal chains, and is based on experimentally measurable parameters relevant to PLMs. The model predicts interparticle attractions due to micellar bridging that are stronger and longer-range than those encountered in ordinary telechelic polymers. Mapping the analytical potential onto the more familiar Double Yukawa potential allows, for the first time, accurate, a priori prediction of suspension microstructure and phase behavior when compared to experimental data for model nanoparticles dispersed in wormlike micelles over a range of solution conditions.     

The story of clopidogrel and its predecessor,ticlopidine: Could these major antiplatelet and antithrombotic drugs be discovered and developed today?

Clopidogrel and its predecessor, ticlopidine, are thienopyridine derivatives that inhibit platelet activation and aggregation by irreversibly blocking the ADP P2Y12 receptor. They are indicated for the reduction of atherothrombotic events in cardiovascular patients. Clopidogrel has a more favorable side effect profile than ticlopidine. These two molecules could not be discovered today through an in vitro high throughput screening because they are prodrugs, which must be transformed in the body into an active metabolite. The active metabolite is very unstable and cannot be obtained by chemical synthesis or stored. Moreover, its structure cannot be predicted by rational drug design. Even if these two prodrugs were discovered today by chance, they would probably not be developed by the majority of R&D teams because of a number of drawbacks associated with their strong metabolic transformation in the body and their irreversible effect on platelets.     

Improvement of the Chemometric Variety Characterization of Wines by Improving the Detection Limit for Aroma Compounds

Headspace–SPME followed by capillary gas chromatography/mass spectrometry was used to investigate 90 German wines originating from different grape varieties, vintages, and growing areas. Aromagrams obtained in single ion monitoring (SIM) and in the full scan detection mode (SCAN) of quadrupole mass spectrometer were compared. Detection limits, reproducibility, and linearity for some aroma relevant substances were estimated over a wide concentration range. The advantages of SIM data set (lower detection limit, better reproducibility and linearity in the smaller concentration ranges) should be reflected in more reliable results in classification of wines. To verify these expectation, classification of variety by discriminant analysis was performed with cross validation using both SIM and SCAN data sets including 19 aroma compounds, respectively.     

Six-dimensional quantum dynamics of dissociative chemisorption of H2 on Ru(0001)

Six-dimensional quantum dynamics calculations on dissociative chemisorption of H(2) on Ru(0001) are performed. The six-dimensional potential energy surface is generated using density functional theory. Two different generalized gradient approximations are used, i.e., RPBE and PW91, to allow the results to be compared. The dissociation probability for normally incident H(2) on a clean Ru(0001) surface is calculated. Large differences between the reaction probabilities calculated using the RPBE and PW91 are seen, with the PW91 results showing a much narrower reaction probability curve and a much higher reactivity. Using the reaction probabilities and assuming normal energy scaling reaction rates are generated for temperatures between 300 and 800 K. The rate generated using the PW91 results is higher by about a factor 5 than the rate based on the RPBE results in the range of temperatures relevant to ammonia production.     

Robust regression methods to calibrate a continuous flow analyzer in the colorimetric analysis of inorganic phosphorus in seawater

The presence of a salinity effect in the automated analysis of phosphorus in seawater performed by a phosphomolybdate complex can cause the inaccurate estimation of the true amount, because the calibration procedure performed by least-squares regression does not take into account the different analytical response of samples and standard solutions. The error arising from this salt effect is corrected by calibrating the autoanalyzer with robust regression methods (RRMs), which allow definition of the range of salinity in which the analytical response of the autoanalyzer is only dependent on the concentration of marine nutrients. The RRMs are especially helpful in the analysis of oligotrophic samples where the salinity effect is particularly relevant.     

Highly Resolved Pure-Shift Spectra on a Compact NMR Spectrometer

Benchtop NMR spectrometers experience a great success for a wide range of applications. However, their performance is highly limited by peak overlaps. Emerging “pure-shift NMR” (PS NMR) methods have been intensively used at high field to enhance the resolution by homodecoupling strategies. Here, different PS methods have been implemented on a compact NMR spectrometer operating at 43 MHz. Among the PS methods, the recent PSYCHE scheme appears more sensitive than Zangger-Sterk (ZS) experiments and offers a substantial resolution improvement as compared to 1D ¹H. On the other hand, despite their slightly lower sensitivity, ZS methods are more efficient to reduce broad signals and are more immune to strong couplings. Finally, the classical J-resolved pulse sequence is more efficient to reduce larger signals for bigger-sized molecules. The three approaches appear relevant for benchtop NMR and their combination forms an efficient toolbox to analyze a great diversity of samples.     

Two-dimensional Monte Carlo studies of lipid molecules in a bilayer membrane

We present a new model to study in-plane liquid properties of lipid membranes. The different conformations of lipids are represented by a seven-state system of hard triatomic particles, or triples, of varying lengths which correspond to the different cross-sectional areas of the lipids in the plane of the membrane. Two-dimensional Monte Carlo simulations are performed in both the constant NVT and NPT ensembles. The distribution of states has a strong density dependence and a small temperature dependence over the biologically relevant range. There is no long range orientational order in the systems before freezing. The short range orientational order increases with density. Widom's particle insertion method is used to obtain the excess chemical potential of the system for the seven states. These values, along with the pressure, are in excellent agreement with estimates from scaled particle theory.     

Proteomics in cancer research: methods and application of array-based protein profiling technologies

With the human genome sequence now determined, the field of molecular medicine is moving beyond genomics to proteomics, the large-scale analysis of proteins.It is now possible to examine the expression of more than 1000 proteins using mass spectrometry technology coupled with various separation methods.Microarray technology is a new and efficient approach, for extracting relevant biomedical data and has a wide range of applications. It provides a versatile tool to study protein-protein, protein-nucleic acid, protein-lipid, enzyme-substrate and protein-drug interactions.This review paper will explore the key themes in proteomics and their application in clinical cancer research.     

Temperature dependent Raman scattering study of l-ascorbic acid

Temperature dependent Raman study of l-ascorbic acid has been performed from 15 to 418 K. Changes in the wavenumber vs. temperature plots for some internal modes were interpreted as conformational molecular change and the discontinuity in the wavenumber vs. temperature plots along with the appearance of a new vibrational mode in the temperature range 200-270 K suggests that l-ascorbic acid undergoes a structural phase transition. For temperatures higher than 300 K, no relevant modification was observed on the Raman spectra thus indicating a stable structure at high temperatures. Additionally, a correlation between OH stretching wavenumber and the behavior of hydrogen bond is also made.