pH-Dependent Behavior of Hydrophobically Modified Polyelectrolyte Shells of Polymeric Nanoparticles

Summary: The self-assembled core-shell nanoparticles based on fluorescently double-tagged high-molar-mass polystyrene-block-poly(methacrylic acid), PS-PMA, were prepared in aqueous buffers by dialysis from 1,4-dioxane – water mixtures. The conformations of shell-forming PMA chains were studied using nonradiative excitation energy transfer measurements. The study shows that two populations of distinctly different conformations (collapsed and stretched) coexist in the shell and their ratio depends on pH.     

Concrete Quantum Logics and Δ -Logics,States and Δ -States

By a concrete quantum logic (in short, by a logic) we mean the orthomodular poset that is set-representable. If \(L=({\Omega },\mathcal {L})\) is a logic and \(\mathcal {L}\) is closed under the formation of symmetric difference, Δ , we call L a Δ -logic. In the first part we situate the known results on logics and states to the context of Δ -logics and Δ -states (the Δ -states are the states that are subadditive with respect to the symmetric difference). Moreover, we observe that the rather prominent logic \(\mathcal {E}^{\text {even}}_{\Omega }\) of all even-coeven subsets of the countable set Ω possesses only Δ -states. Then we show when a state on the logics given by the divisibility relation allows for an extension as a state. In the next paragraph we consider the so called density logic and its Δ -closure. We find that the Δ -closure coincides with the power set. Then we investigate other properties of the density logic and its factor.     

Finite BRST Mapping in Higher-Derivative Models

We continue the study of finite field-dependent BRST (FFBRST) symmetry in the quantum theory of gauge fields. An expression for the Jacobian of path integral measure is presented, depending on a finite field-dependent parameter, and the FFBRST symmetry is then applied to a number of well-established quantum gauge theories in a form which incudes higher-derivative terms. Specifically, we examine the corresponding versions of the Maxwell theory, non-Abelian vector field theory, and gravitation theory. We present a systematic mapping between different forms of gauge-fixing, including those with higher-derivative terms, for which these theories have better renormalization properties. In doing so, we also provide the independence of the S-matrix from a particular gauge-fixing with higher derivatives. Following this method, a higher-derivative quantum action can be constructed for any gauge theory in the FFBRST framework.     

Large Time Asymptotics for the Kadomtsev–Petviashvili Equation

We study the large time asymptotic behavior of solutions to the Kadomtsev–Petviashvili equations $$\left\{\begin{array}{ll} u_{t} + u_{xxx} + \sigma \partial_{x}^{-1}u_{yy} = -\partial_{x}u^{2}, \quad \quad (x, y) \in {\bf R}^{2}, t \in {\bf R},\\ u(0, x, y) = u_{0}( x, y), \, \quad \quad \qquad \qquad (x, y) \in {\bf R}^{2},\end{array}\right.$$ where σ = ±1 and \({\partial_{x}^{-1} = \int_{-\infty}^{x}dx^{\prime} }\) . We prove that the large time asymptotics of the derivative u _x of the solution has a quasilinear character.     

ELENA: the extra low energy anti-proton facility at CERN

At the last LEAP conference in Vancouver 2011 the authors stated that a project ”ELENA”, as an abbreviation for Extra Low ENergy Antiproton ring and as first discussed in 1982 for LEAR by H. Herr et al., was freshly proposed with a substantial new design and revised layout and that it was under consideration to be built at CERN. ELENA is an upgrade of the Anti-proton Decelerator (AD) at CERN and is devoted to special experiments with physics using low energy anti-protons. The main topics are the anti-hydrogen production and consecutive studies of the features of this anti-matter atom as well as the anti-proton nucleon interaction by testing the QED to high precision. During the last years the project underwent several steps in presentations at different committees at CERN and was finally approved such that the construction has started. ELENA will increase the number of useful anti-protons by about two orders of magnitude and will allow to serve up to four experiments simultaneously. Very first and convincing results from the experiments at the AD have been published recently. For high precision physics, however, it appears to be cumbersome, time consuming and ineffective when collecting the needed large numbers and high densities of anti-proton clouds with the present AD. Both the effectiveness and the availability for additional experiments at this unique facility will drastically increase, when the anti-proton beam of presently 5 MeV kinetic energy is reduced by the additional decelerator ELENA to 100 keV.     

Decomposition of in vivo spatially offset Raman spectroscopy data using multivariate analysis techniques

The decomposition of spatially offset Raman spectra for complex multilayer systems, such as biological tissues, requires advanced techniques such as multivariate analyses. Often, in such situations, the decomposition methods can reach their limits of accuracy well before the limits imposed by signal‐to‐noise ratios. Consequently, more effective reconstruction methods could yield more accurate results with the same data set. In this study we process spatially offset Raman spectroscopy (SORS) data with three different multivariate techniques (band‐target entropy minimization (BTEM), multivariate curve resolution and parallel factor analysis (PARAFAC)) and compare their performance when analysing a spectrally challenging plastic model system and an even more challenging problem, the analysis of human bone transcutaneously in vivo. For the in vivo measurements, PARAFAC's requirement of multidimensional orthogonal data is addressed by recording SORS spectra both at different spatial offsets and at different anatomical points, the latter providing added dimensionality through the variation of skin/soft tissue thickness. The BTEM and PARAFAC methods performed the best on the plastic system with the BTEM more faithfully reconstructing the major Raman bands and PARAFAC the smaller more heavily overlapped features. All three methods succeeded in reconstructing the bone spectrum from the transcutaneous data and gave good figures for the phosphate‐to‐carbonate ratio (within 2% of excised human tibia bone); the PARAFAC gave the most accurate figure for the mineral‐to‐collagen ratio (20% less than excised human tibia bone). Previous studies of excised bones have shown that certain bone diseases (such as osteoarthritis, osteoporosis and osteogenesis imperfecta) are accompanied by compositional abnormalities that can be detected with Raman spectroscopy, the utility of a technique which could reconstruct bone spectra accurately is manifest. The results have relevance on the use of SORS in general. © 2014 Crown copyright. Journal of Raman Spectroscopy published by John Wiley & Sons, Ltd.     

Stereoselective palladium-catalyzed functionalization of homoallylic alcohols: a convenient synthesis of di- and trisubstituted isoxazolidines and β-amino-δ-hydroxy esters

Enantiopure, Boc-protected alkoxyamines 12 and 13, derived from the readily available homoallylic alcohols 4 via a reaction that involves either inversion or retention of configuration, undergo a diastereoselective Pd-catalyzed ring-closing carbonylative amidation to produce isoxazolidines 16/17 (≤50:1 diastereoisomer ratio (d.r.)) that can be readily converted into the N-Boc-protected esters of β-amino-δ-hydroxy acids and their γ-substituted homologues 37. The key carbonylative cyclization proceeds through an unusual syn addition of the palladium and the nitrogen nucleophile across the C=C bond (19→21), as revealed by the reaction of 15, which afforded isoxazolidine 18 with high diastereoselectivity.     

Structures and cytotoxic properties of cucumariosides H₂, H₃ and H₄ from the sea cucumber Eupentacta fraudatrix

New triterpene glycosides, cucumariosides H? (1), H? (2) and H? (3), have been isolated from the Far Eastern sea cucumber Eupentacta fraudatrix. The structures of 1-3 were elucidated using extensive NMR spectroscopy (1H- and 13C-NMR, DEPT, 1H-1H COSY, 1D TOCSY, H2BC, HMBC, heteronuclear single-quantum coherence, and NOESY) and ESI-MS. Glycosides 1-3 are monosulphated branched pentaosides having rare 3-O-methyl-D-xylose as a terminal monosaccharide. Glycosides 1 and 3 contain holostane aglycones, whereas 2 has a 23,24,25,26,27-pentanorlanostane aglycone with an 18(16)-lactone, which is also uncommon for the sea cucumbers. Glycoside 3 contains a very rare ethoxyl radical at C-25 of the aglycone side chain, and it is most probably an artefact that was formed during long storage of the ethanolic extract. Cytotoxic activities of 1-3 against mouse spleen lymphocytes, haemolytic activity against mouse erythrocytes and Ehrlich carcinoma cells have been studied. The presence of 25-hydroxy group in aglycone moiety significantly decreased the activities.     

ProBiS-database: precalculated binding site similarities and local pairwise alignments of PDB structures

ProBiS-Database is a searchable repository of precalculated local structural alignments in proteins detected by the ProBiS algorithm in the Protein Data Bank. Identification of functionally important binding regions of the protein is facilitated by structural similarity scores mapped to the query protein structure. PDB structures that have been aligned with a query protein may be rapidly retrieved from the ProBiS-Database, which is thus able to generate hypotheses concerning the roles of uncharacterized proteins. Presented with uncharacterized protein structure, ProBiS-Database can discern relationships between such a query protein and other better known proteins in the PDB. Fast access and a user-friendly graphical interface promote easy exploration of this database of over 420 million local structural alignments. The ProBiS-Database is updated weekly and is freely available online at http://probis.cmm.ki.si/database.