Triphilic pentablock copolymers with perfluoroalkyl segment in central position

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.     

Tailoring a Dress to Single Protein Molecules: Proteins Can Do It Themselves through Localized Photo-Polymerization and Molecular Imprinting

Molecularly imprinted polymer nanoparticles (MIP NPs) are antibody-like recognition materials prepared by a template-assisted synthesis. MIP NPs able to target biomolecules, like proteins, are under the spotlight for their great potential in medicine, but efficiently imprinting biological templates is still very challenging. Here we propose generating a molecular imprint in single NPs, by photochemically initiating the polymerization from individual protein templates. In this way, each protein molecule tailors itself its own “polymeric dress”. For this, the template protein is covalently coupled with a photoinitiator, Eosin Y. Irradiated with light at 533 nm, the Eosin moiety acts as an antenna and transfers energy to a co-initiator (an amine), which generates a radical and initiates polymerization. As a result, a polymer network is forming only around the very template molecule, producing cross-linked NPs of 50 nm, with single binding sites showing high affinity (K_D 10⁻⁹ m ) for their biological target, and selectivity over other proteins.     

Two CdII/CoII‐Imidazolate Coordination Polymers: Syntheses,Crystal Structures,Stabilities, and Luminescent/Magnetic Properties

Cadmium(II) based 2D coordination polymer [Cd(L1)₂(DMF)₂] ( 1 ) (L1 = 4,5‐dicyano‐2‐methylimidazolate, DMF = N,N′‐dimethylformamide) and 2D cobalt(II)‐imidazolate framework [Co(L3)₄] ( 2 ) (L3 = 4,5‐diamide‐2‐ethoxyimidazolate) were synthesized under solvothermal reaction conditions. The materials were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X‐ray diffraction measurement (PXRD) and single‐crystal X‐ray diffraction. Compound 1 has hexacoordinate Cd^II ions and forms a zigzag chain‐like coordination polymer structure, whereas compound 2 exhibits a 2D square grid type structure. The thermal stability analysis reveals that 2 showed an exceptional thermal stability up to 360 °C. Also, 2 maintained its fully crystalline integrity in boiling water as confirmed by PXRD. The solid state luminescent property of 1 was not observed at room temperature. Compound 2 showed an independent high spin central Co^II atom.     

Di-tert-butyldiphosphatetrahedrane as a Source of 1,2-Diphosphacyclobutadiene Ligands

Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations.     

Novel Methods to Manipulate Autolysis in Sparkling Wine: Effects on Yeast

Sparkling wine made by the traditional method (Méthode Traditionelle) develops a distinct and desirable flavour and aroma profile attributed to proteolytic processes during prolonged ageing on lees. Microwave, ultrasound and addition of β-glucanase enzymes were applied to accelerate the disruption of Saccharomyces cerevisiae, and added to the tirage solution for secondary fermentation in traditional sparkling winemaking. Scanning electron microscopy and flow cytometry analyses were used to observe and describe yeast whole-cell anatomy, and cell integrity and structure via propidium iodide (PI) permeability after 6-, 12- and 18-months post-tirage. Treatments applied produced features on lees that were distinct from that of the untreated control yeast. Whilst control yeast displayed budding cells (growth features) with smooth, cavitated and flat external cell appearances; microwave treated yeast cells exhibited modifications like ‘doughnut’ shapes immediately after treatment (time 0). Similar ‘doughnut’-shaped and ‘pitted/porous’ cell features were observed on progressively older lees from the control. Flow cytometry was used to discriminate yeast populations; features consistent with cell disruption were observed in the microwave, ultrasound and enzyme treatments, as evidenced by up to 4-fold increase in PI signal in the microwave treatment. Forward and side scatter signals reflected changes in size and structure of yeast cells, in all treatments applied. When flow cytometry was interpreted alongside the scanning electron microscopy images, bimodal populations of yeast cells with low and high PI intensities were revealed and distinctive ‘doughnut’-shaped cell features observed in association with the microwave treatment only at tirage, that were not observed until 12 months wine ageing in older lees from the control. This work offers both a rapid approach to visualise alterations to yeast cell surfaces and a better understanding of the mechanisms of yeast lysis. Microwave, ultrasound or β-glucanase enzymes are tools that could potentially initiate the release of yeast cell compounds into wine. Further investigation into the impact of such treatments on the flavour and aroma profiles of the wines through sensory evaluation is warranted.     

Metal Sulfide Nanoparticle Synthesis with Ionic Liquids – State of the Art and Future Perspectives

Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.     

Tetrahalidometallate(II) Ionic Liquids with More than One Metal: The Effect of Bromide versus Chloride

Fifteen N-butylpyridinium salts – five monometallic [C₄Py]₂[MBr₄] and ten bimetallic [C₄Py]₂[M_0.5^aM_0.5^bBr₄] (M=Co, Cu, Mn, Ni, Zn) – were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10⁻⁵ and 10⁻⁶ S cm⁻¹. At elevated temperatures, the conductivities reach up to 10⁻⁴ S cm⁻¹ at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.     

On Vaporizing Water Flow in Hot Sub-Vertical Rock Fractures

Water injection into unsaturated fractured rock at above-boiling temperatures gives rise to complex fluid flow and heat transfer processes. Examples include water injection into depleted vapor-dominated geothermal reservoirs, and emplacement of heat-generating nuclear wastes in unsaturated fractured rock. We conceptualize fractures as two-dimensional heterogeneous porous media, and use geostatistical techniques to generate synthetic permeability distributions in the fracture plane. Water flow in hot high-angle fractures is simulated numerically, taking into account the combined action of gravity, capillary, and pressure forces, and conductive heat transfer from the wall rocks which gives rise to strong vaporization. In heterogeneous fractures boiling plumes are found to have dendritic shapes, and to be subject to strong lateral flow effects. Fractures with spatially-averaged homogeneous permeabilities tend to give poor approximations for vaporization behavior and liquid migration patterns. Depending on water flow rates, rock temperature, and fracture permeability, liquid water can migrate considerable distances through fractured rock that is at above-boiling temperatures and be only partially vaporized.     

High-order evolution equation for nonlinear wave-packet propagation with surface tension accountingÉquation d'évolution d'ordre élevé de groupes d'ondes non linéaires en présence de tension superficielle

The nonlinear problem for propagation of wave-packets along the interface of two semi-infinite fluids is solved on the basis of multiple scale asymptotic expansions. Unlike all previous investigations dealing only with third-order approximations, here fourth-order approximation is developed. The corresponding solvability condition is obtained and the evolution equation in the case away from the cut-off wave number is derived. As a result, the nonlinear higher-order Schrödinger equation is obtained which contains the nonlinear part in a compact form. This equation is valid for a wide range of wave numbers. The stability diagram shows regions of stability and instability of capillary-gravity wave-packets. To cite this article: I. Selezov et al., C. R. Mecanique 331 (2003).