Bitumen Binders Modified with Sulfur/Organic Copolymers

With the continuing growth of waste sulfur production from the petroleum industry processes, its utilization for the production of useful, low-cost, and environmentally beneficial materials is of primary interest. Elemental sulfur has a significant and established history in the modification of bitumen binders, while the sulfur-containing high-molecular compounds are limited in this field. Herein, we report a novel possibility to utilize the sulfur/organic copolymers obtained via the inverse vulcanization process as modifiers for bitumen binders. Synthesis and thermal characterization (TGA-DSC) of polysulfides derived from elemental sulfur (S₈) and unsaturated organic species (dicyclopentadiene, styrene, and limonene) have been carried out. The performance of modified bitumen binders has been studied by several mechanical measurements (softening point, ductility, penetration at 25 °C, frass breaking point, adhesion to glass and gravel) and compared to the unmodified bitumen from the perspective of normalized requirements concerning polymer-modified bitumen. The interaction of bitumen binder with sulfur/organic modifier has been studied by means of FTIR spectroscopy and DSC measurements. The impact of the modification on the performance properties of bitumen has been demonstrated. The bitumen binders modified with sulfur/organic copolymers are in general less sensitive to higher temperatures (higher softening point up to 7 °C), more resistant to permanent deformations (lower penetration depth), and more resistant to aging processes without intrusive deterioration of parameters at lower temperatures. What is more, the modification resulted in significantly higher adhesion of bitumen binders to both glass (from 25% up to 87%) and gravel surfaces in combination with a lower tendency to form permanent deformations (more elastic behavior of the modified materials).     

From Isostructurality to Structural Diversity of Ag(I) Coordination Complexes Formed with Imidazole Based Bipodal Ligands,and Disclosure of a Unique Topology

Two Ag(I) complexes with 1,3-bis(imidazol-1-ylmethyl)benzene (bib) and counterions BF₄⁻ (1) and PF₆⁻ (2) were synthesized in order to check their behavior in forming molecular/crystal structures. This allows comparison with the final products of analogous syntheses performed with similar bidentate ligands containing methyl substituents on the benzene ring, namely 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene (bimb) and 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (bitmb). The Ag(I) complexes obtained with the methylated ligands mentioned above form isostructural pairs of waved 1D chains or dinuclear boxes, of general formula {[Ag(bimb)]X}_n and [Ag₂(btmb)₂]X₂, respectively (X = BF₄⁻, PF₆⁻), under the same reaction conditions. SCXRD analyses of 1 and 2 revealed the formation of polymeric coordination compounds of formula {[Ag₂(bib)₃](BF₄)₂}_n and {[Ag(bib)]PF₆}_n, respectively, different from those observed for bimb. The 3D coordination polymer 1 forms a unique 5,5-c net of 5,5T188 topological type, observed for the very first time for a coordination compound, with silver cations adopting a trigonal geometry, whereas 2 shows the presence of 1D single-stranded cationic helices with linear coordination of the metal centers. Interestingly, these complexes differ not only from the mentioned isostructural pairs of related Ag(I) complexes, but also from the isostructural pair of compounds obtained as the final product when reacting bib and bimb with the larger counterion CF₃SO₃⁻. Hirshfeld surface analyses indicate a higher contribution of F⋯H intermolecular contacts in 2 than in 1, with H⋯H contacts being dominant in the latter.     

Characterization of Hantavirus N Protein Intracellular Dynamics and Localization

Hantaviruses are enveloped viruses that possess a tri-segmented, negative-sense RNA genome. The viral S-segment encodes the multifunctional nucleocapsid protein (N), which is involved in genome packaging, intracellular protein transport, immunoregulation, and several other crucial processes during hantavirus infection. In this study, we generated fluorescently tagged N protein constructs derived from Puumalavirus (PUUV), the dominant hantavirus species in Central, Northern, and Eastern Europe. We comprehensively characterized this protein in the rodent cell line CHO-K1, monitoring the dynamics of N protein complex formation and investigating co-localization with host proteins as well as the viral glycoproteins Gc and Gn. We observed formation of large, fibrillar PUUV N protein aggregates, rapidly coalescing from early punctate and spike-like assemblies. Moreover, we found significant spatial correlation of N with vimentin, actin, and P-bodies but not with microtubules. N constructs also co-localized with Gn and Gc albeit not as strongly as the glycoproteins associated with each other. Finally, we assessed oligomerization of N constructs, observing efficient and concentration-dependent multimerization, with complexes comprising more than 10 individual proteins.     

Influence of synthesis and processing conditions on the release behavior and stability of sol-gel derived silica xerogels embedded with bioactive compounds

The influence of processing parameters and synthetic strategies in the properties of sol-gel derived silica matrices intended for the release of bioactive compounds was investigated. The time-evolution of the matrix properties during its aging at room temperature in the dry and wet forms was investigated by measuring some of its physical and drug retaining properties. The results indicate that long term gel aging in the wet form is fundamental for the obtainment of dry matrices that are stable upon storage, a fundamental requirement for any practical application. In the case of hybrid matrices obtained by replacing part of the tetraethoxysilane precursor with mono-methyl trimethoxysilane, the order of addition of the reaction component is also important in determining the properties of the final dry gel, probably by influencing the polymer structural properties. This parameter acts synergistically with the matrix composition in determining the release properties of xerogels embedded with bioactive compounds.     

Antisolvent Recrystallization Strategy to Screen Appropriate Carriers to Stabilize Filgotinib Amorphous Solid Dispersions

Drugs in amorphous solid dispersions (ASDs) are highly dispersed in hydrophilic polymeric carriers, which also help to restrain recrystallization and stabilize the ASDs. In this study, microscopic observation after antisolvent recrystallization was developed as a rapid screening method to select appropriate polymers for the initial design filgotinib (FTN) ASDs. Using solvent evaporation, FTN ASDs with the polymers were prepared, and accelerated experimentation validated this screening method. Fourier-transform infrared spectroscopy, Raman scattering, and nuclear magnetic resonance revealed hydrogen-bonding formation in the drug-polymer binary system, which was critical for ASDs stabilization. A Flory-Huggins interaction parameter and water sorption isotherms were applied to evaluate the strength of the interaction between FTN and the polymers. The dissolution rate was also significantly improved by ASDs formulation, and the presence of the polymers exerted solubilization effects. These results suggested the efficacy of this screening method as a preliminary tool for polymer selection in ASDs design.     

Preparation and characterization of co-processed starch/MCC/chitin hydrophilic polymers onto magnesium silicate

It was aimed to investigate the compressibility, compactibility, powder flow and tablet disintegration of a new excipient comprising magnesium (Mg) silicate co-processed (5%–85% w/w) onto chitin, microcrystalline cellulose (MCC) and starch as the hydrophilic polymers of interest. Initially, the mechanism of tablet disintegration was studied by measuring water infiltration rate, moisture sorption, swelling capacity and hydration ability. Moreover, the powders compression behavior was carried out by applying Kawakita model of compression analysis in addition to porosity and radial tensile strength measurements. In vitro drug release of compacts made of 400?mg ibuprofen and 300?mg of the hydrophilic polymers containing 30% w/w Mg silicate co-precipitate was investigated in phosphate buffer (pH 7.8). This work demonstrated that the incorporation of Mg silicate to the hydrophilic polymers lead to the improvement of powder flowability, compactibility, stability (with regard to storage conditions), compacts crushing strength, and disintegration time in addition to faster drug release. The overall findings are practically advantageous in the context of finding a low cost and multifunctional co-processed excipient of natural origins.     

Composites with AIEgens for Temperature Sensing and Strain Measurement

Traditional fluorescent molecules are easily quenched in most solid applications. Materials with aggregation‐induced emission (AIE) characteristics offer a new way to solve this problem. In this paper, polymer composites consisting of tetraphenylethene (TPE) with AIE properties and polydimethylsiloxane (PDMS) are developed by a simple blending method. The prepared material shows a variable fluorescent emission with different TPE concentrations in the polymer matrix. Such a unique phenomenon arises mainly from the transition of the AIEgen from the crystal to the amorphous state. Interestingly, the fluorescent emission of composites is strongly affected by external factors, such as temperature and mechanical conditions, thus giving the material a stimuli‐sensitive fluorescence property. Specifically, the fluorescence intensity of composites decreases with an increasing temperature, and the same response exhibits when the mechanical force is applied to the material. The excellent response of composites to the temperature and mechanical deformation guarantees the sensory applications of the developed material.     

Direct Observation of a Cyclic Vinyl Polymer Prepared by Anionic Polymerization using N‐Heterocyclic Carbene and Subsequent Ring‐Closure without Highly Diluted Conditions

A 1:1 adduct of methyl sorbate (MS) and 1,3‐di‐tert‐butylimidazol‐2‐ylidene (NHCtBu) initiates anionic polymerization of a nonconjugated polar alkene, allyl methacrylate (AMA) in toluene at ?20 °C. After the monomer is consumed quantitatively using a bulky aluminum Lewis acid, methylaluminum bis(2,6‐di‐tert‐butyl‐4‐methylphenoxide) (MAD), as an additive, successive ring‐closure occurs without highly dilute conditions to give a cyclic poly(AMA) containing α‐terminal MS unit, and an M_n of 8.8 × 10³?58.5 × 10³ with a narrow molecular dispersity index (M_w/M_n = 1.1₄–1.3₇). The lack of a need for dilution is due to the fact that an α‐terminal NHCtBu group is acting as the counter cation for the propagating center in the polymerization. From ¹H NMR and matrix assisted laser desorption/ionization (MALDI‐TOF) mass spectra, combined with transmittance electron microscope (TEM) observation of a synthesized poly(AMA) with longer alkyl side chains prepared via a thiol‐ene click reaction, it is concluded that once the monomer is consumed, nucleophilic attack at the neighboring methine of the α‐terminal NHCtBu residue by the propagating anionic center causes ring‐closing to cyclic poly(AMA).     

Kinetic Investigations of Quaternization Reactions of Poly[2‐(dimethylamino)ethyl methacrylate] with Diverse Alkyl Halides

Kinetic investigations of the quaternization reactions of poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) with alkyl halides (1‐iodobutane, 1‐iodoheptane, and 1‐iododecane) are carried out at different temperatures. For this purpose, a PDMAEMA (M_n = 17.8 kDa, Ð = 1.35) synthesized via reversible addition fragmentation chain transfer polymerization is utilized. The progress of the quaternization reactions is followed by proton nuclear magnetic resonance. As expected, the rate of quaternization is higher with increasing temperature. The experimental data are used to determine the following kinetic parameters: order of the reaction, Arrhenius' pre‐exponential factor, and activation energy. To the best of knowledge, this is the first contribution that provides detailed kinetic data of the quaternization reactions on PDMAEMA.     

Photoelectrochemical Bisphenol S Sensor Based on ZnO‐Nanoroads Modified by Molecularly Imprinted Polypyrrole

Molecularly imprinted polymers are important tools for the design of sensors and other molecular recognition based analytical systems. In this paper the development of a photoelectrochemical sensor for selective bisphenol determination is reported. The sensor is based on a glass/ZnO/MIP‐Ppy structure consisting of glass modified by a ZnO layer (glass/ZnO), which is functionalized by molecularly imprinted conducting polymer polypyrrole (MIP‐Ppy). The sensitivity of the sensor to bisphenol is in the range of 0.7–12.5 µm . Selectivity tests to other bisphenolic compounds are performed. Some aspects of a photoinduced response mechanism in glass/ZnO/MIP‐Ppy nanostructures are predicted and discussed.