Synthesis of ‘difficult’ peptide sequences: application of a depsipeptide technique to the Jung-Redemann 10- and 26-mers and the amyloid peptide Aβ(1-42)

Recently a 26-mer peptide 1 incorporating Ser and Thr was described as a ‘difficult’ sequence that could not be synthesized by standard methods. If the first Ser residue was used to incorporate a depsipeptide unit, the resulting hybrid was readily assembled. The 26-mer ester was then converted to the native peptide by an O→N acyl shift. The technique may be general for other systems containing appropriate Ser and Thr units and was demonstrated here for the case of the amyloid peptide Aβ(1-42).     

Reversible repositioning of zinc atoms within single crystals of a zinc polycarboxylate with an open-framework structure

Upon dehydration at 220 degrees C under vacuum, an open-framework zinc tetrahydrofuran-2,3,4,5-tetracarboxylate undergoes reversible single crystal to single crystal conversion by some of the zinc atoms moving to different positions that are 3 A away. The reverse process occurs at room temperature by exposing dehydrated crystals to air.     

Saturated amine oxides: Part 8. Hydroacridines: Part 27. Effects of N-oxidation and of N-quaternization on the 15N NMR chemical shifts of N-methylpiperidine-derived mono-, bi-, and tricycloaliphatic tertiary amines

The (15)N chemical shifts of 13 N-methylpiperidine-derived mono-, bi- and tricycloaliphatic tertiary amines, their methiodides and their N-epimeric pairs of N-oxides were measured, and the contributions of specific structural parameters to the chemical shifts were determined by multilinear regression analysis. Within the examined compounds, the effects of N-oxidation upon the (15)N chemical shifts of the amines vary from +56 ppm to +90 ppm (deshielding), of which approx. +67.7 ppm is due to the inductive effect of the incoming N(+)--O(-) oxygen atom, whereas the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The effects of quaternization vary from -3.1 ppm to +29.3 ppm, of which approx. +8.9 ppm is due to the inductive effect of the incoming N(+)--CH(3) methyl group, and the rest is due to the additive shift effects of the various C-alkyl substituents of the piperidine ring. The shift effects of the C-alkyl substituents in the amines, the N-oxides and the methiodides are discussed.     

Competitive ion complexation to polyelectrolytes: determination of the stepwise stability constants. The Ca2+/H+/polyacrylate system

This work presents a new methodology aimed at obtaining the stepwise stability constants corresponding to the binding of ions (or other small molecules) to macromolecular ligands having a large number of sites. For complexing agents with a large number of sites, very simple expressions for the stepwise stability constants arise. Such expressions are model-independent; that is, they allow the determination of the stepwise stability constants without making any previous assumption of the detailed complexation mechanism. The formalism is first presented for a single complexing ion and further extended to competitive systems where the competing ions can display, in general, different stoichiometric relationships. These ideas are applied to the analysis of experimental titrations corresponding to competitive binding of calcium ions to poly(acrylic acid) for different pH values and ionic strengths. Intrinsic stability constants were estimated from the stepwise stability constants (by removing the corresponding statistical factor), and split into specific and electrostatic contributions (by means of the Poisson-Boltzmann equation). After this treatment, the specific proton binding energies showed almost no dependence on the coverage and ionic strength. Likewise, for the range of concentrations studied, the specific component of the intrinsic stability constants of the calcium ions, calculated assuming bidentate binding of Ca to neighboring groups of a linear chain, is almost independent of the calcium and proton coverage and ionic strength.     

Total Synthesis of the Escherichia coli O111 O‐Specific Polysaccharide Repeating Unit

The first total synthesis of the O‐antigen pentasaccharide repeating unit from Gram‐negative bacteria Escherichia coli O111 was achieved starting from four monosaccharide building blocks. Key to the synthetic approach was a bis‐glycosylation reaction to combine trisaccharide 10 and colitose 5 . The colitose building block ( 5 ) was obtained de novo from non‐carbohydrate precursors. The pentasaccharide was equipped at the reducing end with an amino spacer to provide a handle for subsequent conjugation to a carrier protein in anticipation of immunological studies.     

Steady Periodic Water Waves with Unbounded Vorticity: Equivalent Formulations and Existence Results

In this paper we consider the steady water wave problem for waves that possess a merely \(L_r\) -integrable vorticity, with \(r\in (1,\infty )\) being arbitrary. We first establish the equivalence of the three formulations – the velocity formulation, the stream function formulation, and the height function formulation – in the setting of strong solutions, regardless of the value of \(r\) . Based upon this result and using a suitable notion of weak solution for the height function formulation, we then establish, by means of local bifurcation theory, the existence of small-amplitude capillary and capillary–gravity water waves with an \(L_r\) -integrable vorticity.     

Synthesis of nonionic-anionic colloidal systems based on alkaline and ammonium beta-nonylphenol polyethyleneoxy (n = 3-20) propionates/dodecylbenzenesulfonates with prospects for food hygiene

ABSTRACT: BACKGROUND: The main objective of this work was to obtain a binary system of surface-active components (nonionic soap -- alkaline and/or ammonium dodecylbenzenesulfonate) with potential competences in food hygiene, by accessing a scheme of classical reactions (cyanoethylation, total acid hydrolysis and stoichiometric neutralization with inorganic alkaline and/or organic ammonium bases) adapted to heterogeneously polyethoxylated nonylphenols (n = 3-20).In the processing system mentioned, dodecylbenzenesulfonic acid, initially the acid catalyst for the exhaustive hydrolysis of beta-nonylphenolpolyethyleneoxy (n = 3-20) propionitriles, becomes together with the nonionic soap formed the second surface-active component of the binary system. RESULTS: In the reaction scheme adopted the influence of the main operating (duration, temperature, molar ratio of reagents) and structural parameters (degree of oligomerization of the polyoxyethylene chain) on the processing yields for the synthetic steps was followed. The favorable role of the polyoxyethylene chain size is remarked, through its specific conformation and its alkaline cations sequestration competences on the yields of cyanoethylation, but also the beneficial influence of phase-transfer catalysts in the total acid hydrolysis step. The chemical stability of dodecylbenzenesulfonic acid (DBSH) at the temperature and strongly acidic pH of the reaction environment is confirmed. The controlled change of the amount of DBSH in the final binary system will later confer it potential colloidal competences in food hygiene receipts. CONCLUSIONS: The preliminary synthetic tests performed confirmed the prospect of obtaining a broad range of useful colloidal competences in various food hygiene scenarios.     

The Heat Kernel for Kolmogorov Type Operators and its Applications

There are two parts of this article. We first find explicit formulas for the heat kernel of the sub-elliptic operators $\frac{1}{2}\partial_{x}^{2}-x^{m}\partial_{y}$ with m=0,1,2. We also find the heat kernel for the sub-elliptic operator $\frac{1}{2}\sum_{j=1}^{n}\partial_{x_{j}}^{2}+(\sum_{j=1}^{n}a_{j}x_{j})\partial_{y}$ , with a _i constants. In the second part of this paper, we apply results from the first part to construct a close form formula for pricing Asian options on a geometric moving average.     

Mapping the Distribution of Melanin Concentration in Different Fitzpatrick Skin Types Using Hyperspectral Imaging Technique

Measuring skin melanin concentration in order to assess skin phototype according to Fitzpatrick's classification is a constant research goal. In this study, a new approach for assessing skin melanin concentration based on hyperspectral imaging combined with an appropriate analytical model that exploits specific spectral bands to generate maps of melanin content distribution on different Fitzpatrick skin phototypes is presented. Hyperspectral images from the proximal inner side of the forearms of 51 young volunteers covering the first four classes of Fitzpatrick's phototypes were acquired using a hyperspectral imaging system. The images were analyzed using a modified Beer–Lambert law that segregates the contribution of melanin from the other constituents to the skin absorption spectrum. The performance of the model was evaluated using the coefficient of determination (r-squared). The results revealed that the approach proposed in this study generated accurate melanin concentration distribution maps that allowed a correct classification of skin phototype. In conclusion, the proposed approach for assessing skin melanin concentration proved to be very reliable for classifying skin phototypes, and, as it provides maps that are easily read, it has the advantage of a possible extension of its applications to other research concerning skin pigmentation.