Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT⁴⁺ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.     

Isothermal Titration Calorimetry Study of a Bistable Supramolecular System: Reversible Complexation of Cryptand[2.2.2] with Potassium Ions

Isothermal titration calorimetry (ITC) is used to investigate the thermodynamics of the complexation of potassium ions by 1,10‐diaza‐4,7,13,16,21,24‐hexaoxabicyclo[8.8.8]hexacosane (cryptand[2.2.2]) in aqueous solution. By changing the pH of the solution it was possible to trigger the reversible complexation/decomplexation of the cryptand in consecutive in situ experiments and to assess for the first time the use of ITC to monitor the thermodynamics of a bistable system.     

Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer

The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l-lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d-lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth (G) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d-lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d-lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications.     

Characterization of Biocatalysts Prepared with Thermomyces lanuginosus Lipase and Different Silica Precursors,Dried using Aerogel and Xerogel Techniques

The use of lipases in industrial processes can result in products with high levels of purity and at the same time reduce pollutant generation and improve both selectivity and yields. In this work, lipase from Thermomyces lanuginosus was immobilized using two different techniques. The first involves the hydrolysis/polycondensation of a silica precursor (tetramethoxysilane (TMOS)) at neutral pH and ambient temperature, and the second one uses tetraethoxysilane (TEOS) as the silica precursor, involving the hydrolysis and polycondensation of the alkoxide in appropriate solvents. After immobilization, the enzymatic preparations were dried using the aerogel and xerogel techniques and then characterized in terms of their hydrolytic activities using a titrimetric method with olive oil and by the formation of 2-phenylethyl acetate in a transesterification reaction. The morphological properties of the materials were characterized using scanning electron microscopy, measurements of the surface area and pore size and volume, thermogravimetric analysis, and exploratory differential calorimetry. The results of the work indicate that the use of different silica precursors (TEOS or TMOS) and different drying techniques (aerogel or xerogel) can significantly affect the properties of the resulting biocatalyst. Drying with supercritical CO₂ provided higher enzymatic activities and pore sizes and was therefore preferable to drying, using the xerogel technique. Thermogravimetric analysis and differential scanning calorimetry analyses revealed differences in behavior between the two biocatalyst preparations due to the compounds present.     

Chemical composition and antioxidant activity of sulphated polysaccharides extracted from Fucus vesiculosus using different hydrothermal processes

Sulphated polysaccharides (SP) were extracted from Fucus vesiculosus seaweed by using two different hydrothermal processes: microwave-assisted extraction (MAE) and autohydrolysis (AH). The extraction yields, chemical composition, and antioxidant activity of the polysaccharides extracted were determined and compared. Although both processes afforded SP with similar yields (18.2 mass % and 16.5 mass %, for MAE and AH, respectively) and l-fucose as the main monosaccharide, the heterogeneous structure of the polysaccharide recovered was significantly affected by the AH process. The SP obtained by MAE contained 53.8 mole % of fucose, 35.3 mole % of xylose, and 10.8 mole % of galactose; while the SP obtained by AH was composed of 76.8 mole % of fucose and 23.2 mole % of galactose. Both samples presented comparable values of antioxidant activity by the di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium (2,2-diphenyl-1-picrylhydrazyl, DPPH), 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS), and lipid oxidation inhibition methods, but the polysaccharide obtained by AH exhibited a higher antioxidant potential by the differential pulse voltammetry technique. This study demonstrates that the chemical composition and antioxidant activity of SP obtained from F. vesiculosus vary according to the process used for their extraction. However, the SP obtained by MAE or AH both have the potential for use as natural antioxidants in industrial applications.     

Microwave hydrothermal synthesis,characterisation, and catalytic performance of Zn1−x Mn x O in cellulose conversion

Wurtzite-type Zn_1?x Mn _x O (x = 0, 0.03, 0.05, 0.07) nanostructures were successfully synthesised using a simple microwave-assisted hydrothermal route and their catalytic properties were investigated in the cellulose conversion. The morphology of the nanocatalysts is dopant-dependent. Pure ZnO presented multi-plate morphology with a flower-like shape of nanometric sizes, while the Zn_0.97Mn_0.03O sample is formed by nanoplates with the presence of spherical nanoparticles; the Zn_0.95Mn_0.05O and Zn_0.93Mn_0.07O samples are mainly formed by nanorods with the presence of a small quantity of spherical nanoparticles. The catalyst without Mn did not show any catalytic activity in the cellulose conversion. The Mn doping promoted an increase in the density of weak acid sites which, according to the catalytic results, favoured promotion of the reaction.     

Long-Lived Charge-Transfer State Induced by Spin-Orbit Charge Transfer Intersystem Crossing (SOCT-ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long-lived triplet charge-transfer (³CT) state, based on the electron spin control using spin-orbit charge transfer intersystem crossing (SOCT-ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT-ISC takes 8 ns to produce the ³NI* state. Then the slow secondary CS (125 ns) gives the long-lived ³CT state (0.94 μs in deaerated n-hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as ¹NI*→¹CT→³NI*→³CT. With time-resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron-spin polarization pattern was observed for the naphthalimide-localized triplet state. Our spiro compact dyad structure and the electron spin-control approach is different to previous methods for which invoking transition-metal coordination or chromophores with intrinsic ISC ability is mandatory.     

X-Ray Crystallography and Free Energy Calculations Reveal the Binding Mechanism of A2A Adenosine Receptor Antagonists

We present a robust protocol based on iterations of free energy perturbation (FEP) calculations, chemical synthesis, biophysical mapping and X-ray crystallography to reveal the binding mode of an antagonist series to the A_2A adenosine receptor (AR). Eight A_2AAR binding site mutations from biophysical mapping experiments were initially analyzed with sidechain FEP simulations, performed on alternate binding modes. The results distinctively supported one binding mode, which was subsequently used to design new chromone derivatives. Their affinities for the A_2AAR were experimentally determined and investigated through a cycle of ligand-FEP calculations, validating the binding orientation of the different chemical substituents proposed. Subsequent X-ray crystallography of the A_2AAR with a low and a high affinity chromone derivative confirmed the predicted binding orientation. The new molecules and structures here reported were driven by free energy calculations, and provide new insights on antagonist binding to the A_2AAR, an emerging target in immuno-oncology.     

Replacement of the Cobalt Center of Vitamin B12 by Nickel: Nibalamin and Nibyric Acid Prepared from Metal-Free B12 Ligands Hydrogenobalamin and Hydrogenobyric Acid

The (formal) replacement of Co in cobalamin ( Cbl ) by Ni^II generates nibalamin ( Nibl ), a new transition-metal analogue of vitamin B₁₂. Described here is Nibl , synthesized by incorporation of a Ni^II ion into the metal-free B₁₂ ligand hydrogenobalamin ( Hbl ), itself prepared from hydrogenobyric acid ( Hby ). The related Ni^II corrin nibyric acid ( Niby ) was similarly synthesized from Hby , the metal-free cobyric acid ligand. The solution structures of Hbl , and Niby and Nibl , were characterized by spectroscopic studies. Hbl features two inner protons bound at N2 and N4 of the corrin ligand, as discovered in Hby . X-ray analysis of Niby shows the structural adaptation of the corrin ligand to Ni^II ions and the coordination behavior of Ni^II. The diamagnetic Niby and Nibl , and corresponding isoelectronic Co^I corrins, were deduced to be isostructural. Nibl is a structural mimic of four-coordinate base-off Cbls , as verified by its ability to act as a strong inhibitor of bacterial adenosyltransferase.