Biomolecular Densely Grafted Brush Polymers: Oligonucleotides,Oligosaccharides and Oligopeptides

In this Minireview, we describe synthetic polymers densely functionalized with sequence-defined biomolecular sidechains. We focus on synthetic brush polymers of oligonucleotides, oligosaccharides, and oligopeptides, prepared via graft-through polymerization from biomolecule functionalized monomers. The resulting structures are brush polymers wherein a biomolecular graft is positioned at each monomer backbone unit. We describe key synthetic milestones, identify synthetic opportunities, and highlight recent advances in the field, including biological applications.     

Simple one-step ultrasonic synthesis of anatase titania/polypyrrole nanocomposites

In this work, hybrid nanocomposites based on anatase titania:polypyrrole (TiO₂:PPy) were directly obtained from a simple, one-step, ultrasonic (UT)-assisted synthesis. The properties of these crystalline nanocomposites were compared with those of others fabricated using cold (Cold)-assisted synthesis without any UT assistance, which required a hydrothermal treatment (HT) to yield crystalline anatase titania in the nanocomposite (TiO₂:PPy) at low temperature (130 °C) and in a short time (3 h). The SEM results demonstrated that the UT-assisted synthesis is a feasible method to obtain anatase TiO₂:PPy nanocomposites with controlled morphology using low energy. The Fourier transform infrared (FT-IR) bands of the crystalline nanocomposites exhibited a shift with respect to neat components, which was attributed to the strong interaction between the secondary amine groups (N–H) of PPy and the oxygen from TiO₂. The acceptable absorption in the visible region (λ_max = 670 nm) indicates that these nanocomposites are good candidates for harvesting energy in solar cells. Devices based on these nanocomposites were built to evaluate their electrical properties. An increase in the photocurrent was observed for the devices prepared with the nanocomposites from the UT-assisted synthesis.     

Lead and strontium isotopes as indicators for mixing processes of waters in the former mine ‘Himmelfahrt Fundgrube’, Freiberg (Germany)†

To pinpoint the origin and mixing processes of mine waters, different mine water types from the polymetallic sulphide ore deposit ‘Himmelfahrt Fundgrube’ (Freiberg, Germany) were analysed by thermal ionisation mass spectrometry using lead and strontium isotope ratios.

Results show that the lead isotope composition of different mine waters results from a mixture of at least two sources: released lead from oxidised sulphide ores (mainly galena) and anthropogenic lead from groundwater. Furthermore, there are indications for an additional lead source. Strontium isotopes in mine waters identify at least three different sources: released strontium from weathered host rock (Grey Gneisses), released strontium from weathered gangue carbonates, and probably strontium from anthropogenic inputs. Contrary to former oxygen and sulphur isotope studies, strontium isotope compositions as well as hydrochemical parameters show the important role of gangue carbonates as an element source in mine waters.     

Lyapunov functions versus exponential contractions

For nonautonomous linear equations in a Banach space admitting a nonuniform version of exponential contraction, we give an optimal characterization of the exponential behavior in terms of strict Lyapunov sequences. In particular, we construct explicitly strict Lyapunov sequences for each exponential contraction. We also consider the particular case of quadratic Lyapunov functions, and we use the corresponding characterization of the exponential behavior in terms of these functions to show that the stability of an exponential contraction persists under sufficiently small perturbations.     

Parametric estimation of a bivariate stable Lévy process

We propose a parametric model for a bivariate stable Lévy process based on a Lévy copula as a dependence model. We estimate the parameters of the full bivariate model by maximum likelihood estimation. As an observation scheme we assume that we observe all jumps larger than some ε>0 and base our statistical analysis on the resulting compound Poisson process. We derive the Fisher information matrix and prove asymptotic normality of all estimates when the truncation point ε→0. A simulation study investigates the loss of efficiency because of the truncation.     

A sensitive assay for the quantification of morphine and its active metabolites in human plasma and dried blood spots using high-performance liquid chromatography–tandem mass spectrometry

Opioids such as morphine are the cornerstone of pain treatment. The challenge of measuring the concentrations of morphine and its active metabolites in order to assess human pharmacokinetics and monitor therapeutic drugs in children requires assays with high sensitivity in small blood volumes. We developed and validated a semi-automated LC-MS/MS assay for the simultaneous quantification of morphine and its active metabolites morphine 3β-glucuronide (M3G) and morphine 6β-glucuronide (M6G) in human plasma and in dried blood spots (DBS). Reconstitution in water (DBS only) and addition of a protein precipitation solution containing the internal standards were the only manual steps. Morphine and its metabolites were separated on a Kinetex 2.6-μm PFP analytical column using an acetonitrile/0.1% formic acid gradient. The analytes were detected in the positive multiple reaction mode. In plasma, the assay had the following performance characteristics: range of reliable response of 0.25–1000 ng/mL (r ² > 0.99) for morphine, 1–1,000 ng/mL (r ² > 0.99) for M3G, and 2.5–1,000 ng/mL for M6G. In DBS, the assay had a range of reliable response of 1–1,000 ng/mL (r ² > 0.99) for morphine and M3G, and of 2.5–1,000 ng/mL for M6G. For inter-day accuracy and precision for morphine, M3G and M6G were within 15% of the nominal values in both plasma and DBS. There was no carryover, ion suppression, or matrix interferences. The assay fulfilled all predefined acceptance criteria, and its sensitivity using DBS samples was adequate for the measurement of pediatric pharmacokinetic samples using a small blood of only 20–50 μL.     

Analysis of the constituents and quality control of Viola odorata aqueous preparations by HPLC-DAD and HPLC-ESI-MS

In the present study, a method based on liquid chromatography with diode array detection (HPLC-DAD) coupled to an electrospray ionisation (ESI) interface was developed for the determination of the constituents in the aqueous preparations of Viola odorata L. flowering tops. The developed assay was fast, simple and effective and permitted the quality control of the preparations. The aim of this work was to assess the qualitative and quantitative profile of the investigated preparations, which find until today wide applications in food and cosmetic industry, and to propose a validated method for their quality control. Characteristic constituents of V. odorata flowers are considered to be the anthocyanins; however, a detailed literature research showed that data concerning their chemical content are scarce. HPLC-DAD-ESI-MS analyses supported by extensive preparative chromatographic investigations and 2D NMR analyses revealed the predominance of complex flavonol glycosides and permitted the complete characterisation of the content of V. odorata preparations. This is the first report of detailed analysis of the chemical composition of V. odorata flowers.     

A self paired Hopf algebra on double posets and a Littlewood-Richardson rule

Let D be the set of isomorphism types of finite double partially ordered sets, that is sets endowed with two partial orders. On ZD we define a product and a coproduct, together with an internal product, that is, degree-preserving. With these operations ZD is a Hopf algebra. We define a symmetric bilinear form on this Hopf algebra: it counts the number of pictures (in the sense of Zelevinsky) between two double posets. This form is a Hopf pairing, which means that product and coproduct are adjoint each to another. The product and coproduct correspond respectively to disjoint union of posets and to a natural decomposition of a poset into order ideals. Restricting to special double posets (meaning that the second order is total), we obtain a notion equivalent to Stanley's labelled posets, and a Hopf subalgebra already considered by Blessenohl and Schocker. The mapping which maps each double poset onto the sum of the linear extensions of its first order, identified via its second (total) order with permutations, is a Hopf algebra homomorphism, which is isometric and preserves the internal product, onto the Hopf algebra of permutations, previously considered by the two authors. Finally, the scalar product between any special double poset and double posets naturally associated to integer partitions is described by an extension of the Littlewood-Richardson rule.