Temperature induced solubility transitions of various poly(2-oxazoline)s in ethanol-water solvent mixtures

The solution behavior of a series of poly(2-oxazoline)s with different side chains, namely methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, phenyl and benzyl, are reported in ethanol-water solvent mixtures based on turbidimetry investigations. The LCST transitions of poly(2-oxazoline) s with propyl side chains and the UCST transitions of the poly(2-oxazoline) s with more hydrophobic side chains are discussed in relation to the ethanol-water solvent composition and structure. The poly(2-alkyl-2-oxazoline) s with side chains longer than propyl only dissolved during the first heating run, which is discussed and correlated to the melting transition of the polymers

Faster k-Medoids Clustering: Improving the PAM, CLARA, and CLARANS Algorithms

Clustering non-Euclidean data is difficult, and one of the most used algorithms besides hierarchical clustering is the popular algorithm Partitioning Around Medoids (PAM), also simply referred to as k-medoids. In Euclidean geometry the mean-as used in k-means-is a good estimator for the cluster center, but this does not hold for arbitrary dissimilarities. PAM uses the medoid instead, the object with the smallest dissimilarity to all others in the cluster. This notion of centrality can be used with any (dis-)similarity, and thus is of high relevance to many domains such as biology that require the use of Jaccard, Gower, or more complex distances. A key issue with PAM is its high run time cost. We propose modifications to the PAM algorithm to achieve an O(k)-fold speedup in the second SWAP phase of the algorithm, but will still find the same results as the original PAM algorithm. If we slightly relax the choice of swaps performed (at comparable quality), we can further accelerate the algorithm by performing up to k swaps in each iteration. With the substantially faster SWAP, we can now also explore alternative strategies for choosing the initial medoids. We also show how the CLARA and CLARANS algorithms benefit from these modifications. It can easily be combined with earlier approaches to use PAM and CLARA on big data (some of which use PAM as a subroutine, hence can immediately benefit from these improvements), where the performance with high k becomes increasingly important. In experiments on real data with k=100, we observed a 200-fold speedup compared to the original PAM SWAP algorithm, making PAM applicable to larger data sets as long as we can afford to compute a distance matrix, and in particular to higher k (at k=2, the new SWAP was only 1.5 times faster, as the speedup is expected to increase with k)

Thermoresponsive poly(2-oxazoline) block copolymers exhibiting two cloud points: complex multistep assembly behavior

Aqueous solutions of poly(2-oxazoline) block copolymers consisting of a 2-ethyl-2-oxazoline block and a block consisting of a random copolymer of 2-ethyl-2-oxazoline and 2-n-propyl-2-oxazoline (PEtOx-block-P(EtOx-stat-PropOx)) have been studied by dynamic light scattering (DLS), static light scattering (SLS), and turbidimetry. Even at temperatures significantly below the lower critical solution temperature (LCST), polymer unimers are found to coexist with a few large aggregates with an open structure. When heated, the systems exhibit an intricate transmittance behavior whereby the samples becomes visually clear again after an initial cloud point and then exhibit a second cloud point at even higher temperatures. The DLS data indicate that the aggregates formed around the first cloud point restructure and fragment into smaller micelle-like structures ascribed to further dehydration of the more hydrophobic PPropOx containing block, causing the samples to become optically clear again. The observed fragmentation is confirmed by the SLS experiments. At even higher temperatures, both blocks become hydrophobic, causing the formation of large, compact aggregates, resulting in a second cloud point

Efficient cationic ring-opening polymerization of diverse cyclic imino ethers: unexpected copolymerization behavior

The recently developed fast microwave-assisted cationic ring-opening polymerization procedure for 2-oxazolines seems to be ideally suited for slower polymerizing cyclic imino ether monomers. In this study we report the effect of the cyclic imino ether structure on the polymerization rate under exactly the same microwave-assisted conditions revealing that indeed less reactive cyclic imino ethers, including 2-oxazines as well as 4- and 5-substituted 2-oxazolines, can be polymerized to at least 50% conversion for the slowest monomer, namely 5-methyl-2-butyl-2-oxazoline, within 10 h. In addition, the copolymerization behavior of 4-ethyl-2-butyl-2-oxazoline with 2-methyl-2-oxazoline and 2-phenyl-2-oxazoline unexpectedly revealed faster incorporation of the less reactive 4-ethy1-2-buty1-2-oxazoline monomer compared to 2-phenyl-2-oxazoline due to the increased bulk of the latter monomer amplifying the sterical hindrance for polymerization onto the 4-ethyl-2-butyl-2-oxazolinium propagating species

A reverse engineering approach to the suppression of citation biases reveals universal properties of citation distributions

The large amount of information contained in bibliographic databases has recently boosted the use of citations, and other indicators based on citation numbers, as tools for the quantitative assessment of scientific research. Citations counts are often interpreted as proxies for the scientific influence of papers, journals, scholars, and institutions. However, a rigorous and scientifically grounded methodology for a correct use of citation counts is still missing. In particular, cross-disciplinary comparisons in terms of raw citation counts systematically favors scientific disciplines with higher citation and publication rates. Here we perform an exhaustive study of the citation patterns of millions of papers, and derive a simple transformation of citation counts able to suppress the disproportionate citation counts among scientific domains. We find that the transformation is well described by a power-law function, and that the parameter values of the transformation are typical features of each scientific discipline. Universal properties of citation patterns descend therefore from the fact that citation distributions for papers in a specific field are all part of the same family of univariate distributions.Comment: 9 pages, 6 figures. Supporting information files available at http://filrad.homelinux.or

The MCM-Binding Protein ETG1 Aids Sister Chromatid Cohesion Required for Postreplicative Homologous Recombination Repair

The DNA replication process represents a source of DNA stress that causes potentially spontaneous genome damage. This effect might be strengthened by mutations in crucial replication factors, requiring the activation of DNA damage checkpoints to enable DNA repair before anaphase onset. Here, we demonstrate that depletion of the evolutionarily conserved minichromosome maintenance helicase-binding protein ETG1 of Arabidopsis thaliana resulted in a stringent late G2 cell cycle arrest. This arrest correlated with a partial loss of sister chromatid cohesion. The lack-of-cohesion phenotype was intensified in plants without functional CTF18, a replication fork factor needed for cohesion establishment. The synergistic effect of the etg1 and ctf18 mutants on sister chromatid cohesion strengthened the impact on plant growth of the replication stress caused by ETG1 deficiency because of inefficient DNA repair. We conclude that the ETG1 replication factor is required for efficient cohesion and that cohesion establishment is essential for proper development of plants suffering from endogenous DNA stress. Cohesion defects observed upon knockdown of its human counterpart suggest an equally important developmental role for the orthologous mammalian ETG1 protein

On Schubert's Problem of Characteristics

The Schubert varieties on a flag manifold G/P give rise to a cell decomposition on G/P whose Kronecker duals, known as the Schubert classes on G/P, form an additive base of the integral cohomology of G/P. The Schubert's problem of characteristics asks to express a monomial in the Schubert classes as a linear combination in the Schubert basis. We present a unified formula expressing the characteristics of a flag manifold G/P as polynomials in the Cartan numbers of the group G. As application we develop a direct approach to our recent works on the Schubert presentation of the cohomology rings of flag manifolds G/P.Comment: 27page

Two-loop Yang-Mills diagrams from superstring amplitudes

Starting from the superstring amplitude describing interactions among D-branes with a constant world-volume field strength, we present a detailed analysis of how the open string degeneration limits reproduce the corresponding field theory Feynman diagrams. A key ingredient in the string construction is represented by the twisted (Prym) super differentials, as their periods encode the information about the background field. We provide an efficient method to calculate perturbatively the determinant of the twisted period matrix in terms of sets of super-moduli appropriate to the degeneration limits. Using this result we show that there is a precise one-to-one correspondence between the degeneration of different factors in the superstring amplitudes and one-particle irreducible Feynman diagrams capturing the gauge theory effective action at the two-loop level.Comment: 42 pages plus appendices, 10 figure

Mechanisms of Intragastric pH Sensing

Luminal amino acids and lack of luminal acidity as a result of acid neutralization by intragastric foodstuffs are powerful signals for acid secretion. Although the hormonal and neural pathways underlying this regulatory mechanism are well understood, the nature of the gastric luminal pH sensor has been enigmatic. In clinical studies, high pH, tryptic peptides, and luminal divalent metals (Ca2+ and Mg2+) increase gastrin release and acid production. The calcium-sensing receptor (CaSR), first described in the parathyroid gland but expressed on gastric G cells, is a logical candidate for the gastric acid sensor. Because CaSR ligands include amino acids and divalent metals, and because extracellular pH affects ligand binding in the pH range of the gastric content, its pH, metal, and nutrient-sensing functions are consistent with physiologic observations. The CaSR is thus an attractive candidate for the gastric luminal sensor that is part of the neuroendocrine negative regulatory loop for acid secretion