Lower critical solution temperature sensitivity to structural changes in poly(N‐isopropyl acrylamide) homopolymers

The effect of the molecular weight on the lower critical solution temperature (LCST) has been discussed extensively, where LCST increased with molar mass, decreased or kept constant, which leads to confusion. This work is focused on the preparation of poly(N‐isopropyl acrylamide) homopolymers, obtained in a wide molecular weights range. The LCST behavior is analyzed by calorimetry and rheology, and a deep study of molecular features is carried out for a better knowledge of the influence of various parameters involved on LCST. Finally, the molecular weight trend is observed, and its influence on LCST is compared with the effect of other parameters as polymer concentration in water, end‐group effect, and tacticity. It is observed that other parameters such tacticity and end‐group effect will affect the LCST behavior over molecular weight, if this one is not high enough. Furthermore, the study of the LCST ranges will be a useful tool for analyzing the molecular weight trends. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1386–1393     

A new methodology for the determination of silicon in plants by wavelength dispersive X-ray fluorescence

Silicon is an important element for plants at their structure and physiology and plays an important role in bone mineralization and soft tissue development in human beings. Furthermore, its determination is being requested more frequently due to nutritional requirements. However, the methods found in the literature to determine silicon in this type of samples require a sample preparation step, which makes them time-consuming and provides high uncertainties. In this paper, a method for the determination of silicon in plants by wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry has been developed. Horsetail (Equisetum arvense L.) and nettle leaf (Urtica dioica) have been used as a source of silicon due to its medical use. Sample preparation involved calcining the sample at 700°C and preparing fused beads from the calcined sample. Calibration standards for WD-XRF measurement were prepared by mixing certified reference materials and chemical products to reproduce the samples matrix. The linear range for silicon concentration ranges from 6 to 55 wt% SiO₂. The validation of the method was performed measuring a reference material (NCS DC73349 Bush branches and leaves) and comparing the results obtained by WD-XRF with those obtained by an independent method by atomic absorption spectrometry. The developed methodology is rapid and accurate, provides low uncertainties, and is environmentally friendly, as it does require the use of less hazardous reagents.     

Weighted inequalities for some integral operators with rough kernels

In this paper we study integral operators with kernels $$K(x,y) = k_1 (x - A_1 y) \cdots k_m \left( {x - A_m y} \right),$$ $k_i \left( x \right) = {{\Omega _i \left( x \right)} \mathord{\left/ {\vphantom {{\Omega _i \left( x \right)} {\left| x \right|}}} \right. \kern-0em} {\left| x \right|}}^{{n \mathord{\left/ {\vphantom {n {q_i }}} \right. \kern-0em} {q_i }}}$ where Ω _i : ? ⁿ → ? are homogeneous functions of degree zero, satisfying a size and a Dini condition, A _i are certain invertible matrices, and n/q ₁ +…+n/q _m = n?α, 0 ≤ α < n. We obtain the appropriate weighted L ^p -L ^q estimate, the weighted BMO and weak type estimates for certain weights in A(p, q). We also give a Coifman type estimate for these operators.     

TRAJELIX: A Computational Tool for the Geometric Characterization of Protein Helices During Molecular Dynamics Simulations

Summary We have developed a computer program with the necessary mathematical formalism for the geometric characterization of distorted conformations of alpha-helices proteins, such as those that can potentially be sampled during typical molecular dynamics simulations. This formalism has been incorporated into TRAJELIX, a new module within the SIMULAID framework (http://inka.mssm.edu/~mezei/simulaid/) that is capable of monitoring distortions of alpha-helices in terms of their displacement, global and local tilting, rotation around their axes, compression/extension, winding/unwinding, and bending. Accurate evaluation of these global and local structural properties of the helix can help study possible intramolecular and intermolecular changes in the helix packing of alpha-helical membrane proteins, as shown here in an application to the interacting helical domains of rhodopsin dimers. Quantification of the dynamic structural behavior of alpha-helical membrane proteins is critical for our understanding of signal transduction, and may enable structure-based design of more specific and efficient drugs.     

Preparation of a new lightly cross-linked liquid crystalline polyamide by interfacial polymerization. Application to the obtainment of microcapsules with photo-triggered release

Microcapsules based on a new liquid crystalline lightly cross-linked polyamide, in which the state of order can be triggered by means of external stimuli, such as temperature and light, were prepared by interfacial polymerization. This polyamide exhibited a nematic phase up to 166 °C and it started to decompose at 340 °C; morphological variations of the film were observed by Scanning Electron Microscopy in correspondence to the clearing temperature; moreover, by continuous irradiation with UV light at room temperature, the polymer underwent E–Z photoisomerization. The prepared microcapsules contained either toluene, or concentrated solutions of naphthalene or β-carotene, as the core; in all cases, their outer surface appeared smooth and dense, while heterogeneities could be seen on the inner face. Capsule diameter lay in the range 30–120 μm, depending on the encapsulated material, with quite narrow size distributions. To the authors’ knowledge, this is the first example of microcapsules whose shell is completely constituted by a liquid crystalline lightly cross-linked polymer. Release experiments of β-carotene were performed in water and in tetrahydrofuran. β-Carotene release in water at 20 °C was strongly influenced by UV irradiation: in the absence of irradiation, it was practically negligible while, when microcapsules were submitted to continuous irradiation with UV light, β-carotene was quickly released and reached 100% release after 5 min. Preliminary experiments concerning the effect of temperature and of a swelling solvent, such as THF, on release, were also performed.     

Isotope dilution-thermal ionisation mass spectrometric analysis for tin in a fly ash material

Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) analysis has been applied to the determination of tin in a fly ash sample supplied by the EC Joint Research Centre (Ispra, Italy). The proposed procedure includes the silica gel/phosphoric acid technique for tin thermal ionisation activation and a strict heating protocol for isotope ratio measurements. Instrumental mass discrimination factor has been previously determined measuring a natural tin standard solution. Spike solution has been prepared from ¹¹²Sn-enriched metal and quantified by reverse isotope dilution analysis. Two sample aliquots were spiked and tin was extracted with 4.5 M HCl during 25 min ultrasound exposure time. Due to the complex matrix of this fly ash material, a two-step purification stage using ion-exchange chromatography was required prior TIMS analysis. Obtained results for the two sample-spike blends (10.11 ± 0.55 and 10.50 ± 0.64 μmol g⁻¹) are comparable, both value and uncertainty. Also a good reproducibility is observed between measurements. The proposed ID-TIMS procedure, as a primary method and due to the lack of fly ash reference materials certified for tin content, can be used to validate more routine methodologies applied to tin determination in this kind of samples.     

Improved diffusion Monte Carlo propagators for bosonic systems using Itô calculus

The construction of importance sampled diffusion Monte Carlo (DMC) schemes accurate to second order in the time step is discussed. A central aspect in obtaining efficient second order schemes is the numerical solution of the stochastic differential equation (SDE) associated with the Fokker-Plank equation responsible for the importance sampling procedure. In this work, stochastic predictor-corrector schemes solving the SDE and consistent with It? calculus are used in DMC simulations of helium clusters. These schemes are numerically compared with alternative algorithms obtained by splitting the Fokker-Plank operator, an approach that we analyze using the analytical tools provided by Ito; calculus. The numerical results show that predictor-corrector methods are indeed accurate to second order in the time step and that they present a smaller time step bias and a better efficiency than second order split-operator derived schemes when computing ensemble averages for bosonic systems. The possible extension of the predictor-corrector methods to higher orders is also discussed.     

Vacuum-UV-photolysis of aqueous solutions of citric and gallic acids

The vacuum-UV- (VUV-) photolysis of water is one of the advanced oxidation processes (AOP) based on the production of hydroxyl radicals (HO) that can be applied to the degradation of organic pollutants in aqueous systems. The kinetics of the VUV-photolyses of aqueous solutions of citric acid (1) or gallic acid (2) were investigated in the presence or absence of dissolved molecular oxygen (O₂) and under different pH conditions. In the case of 1, the rate of consumption of the substrate was faster at pH 3.4 than in alkaline solution (pH 11), whereas, in the case of 2, the variation of pH (2.5–7.5) did not affect the course of the reaction. Unexpectedly, the rates of depletion of both 1 and 2 decreased in the absence of O₂, this effect being much more pronounced in the case of 2. In order to explain these results, possible reaction pathways for the degradation of 1 and 2 are proposed, and the roles of the oxidizing (HO) and reducing (H and e_aq⁻) species produced by the VUV-photolysis of water are discussed.