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The synthesis of defined triphilic terpolymers with hydrophilic, lyophilic, and fluorophilic blocks is an important challenge as a basis for the development of multicompartment self-assembled structures with potential for, e.g., cascade catalysis and multidrug loading. The synthesis of fluorophilic poly(2-oxazoline)s generally suffers from a very low reactivity of fluorinated 2-oxazoline monomers in cationic ring-opening polymerization (CROP). We report a systematic study on overcoming the extremely low reactivity of 2-perfluoroalkyl-2-oxazolines in CROP by the insertion of methyl and ethyl hydrocarbon spacers between the 2-oxazoline ring and the trifluoromethyl group. The kinetic studies showed the gradual increase of the rate of polymerization with increasing of the hydrocarbon spacer length. The monomer with an ethyl spacer was found to have similar reactivity as 2-alkyl-2-oxazolines and allowed the synthesis of defined triphilic triblock copolymers.

Sultones, the cyclic esters of hydroxyl sulfonic acids, are a fascinating class of heterocycles and the recent years have witnessed an increasing interest in these molecules, especially in six-ring δ-sultones. The importance of these compounds is either because of their biological properties themselves or due to their versatility as intermediates in more complex target syntheses. Accordingly, the development of new synthesis methods to access δ-sultones is an important and rewarding task which we wish to highlight in this review. Graphical abstract

International audience; Objective The aim of our study is to develop amine-free photoinitiating systems (PISs) for the polymerization of representative dental methacrylate resins under blue light irradiation. PISs based on camphorquinone (CQ)/sulfinate and CQ/sulfonate, eventually in combination with an iodonium salt, are proposed and compared to the well-established CQ/amine system. The polymerization performances of thick (1.4 mm) samples of different methacrylate blends upon exposure to a commercial blue LED centered at 477 nm under air are described. Finally, the performances of the new developed PISs are evaluated for dental composites application. Methods FTIR is used to monitor the photopolymerization profiles. ESR spectroscopy and electrochemical experiments are used to identify the radicals generated. Mechanical properties measurements and color stability measurements are carried out to determine the key properties of the dental composites prepared. Results and Significiance The performances of the new proposed PISs for the photopolymerization of thick (1.4 mm) samples of methacrylate upon exposure to a blue dental LED under air are excellent. Similar or better performances and bleaching properties are obtained with the new proposed amine-free systems compared to those reached with the CQ/amine reference system. Dental composites with excellent mechanical properties and exceptional color stability are obtained. The involved chemical mechanisms for the initiation step were also established.

'Green rust' intercalated with aromatic sulfonates can potentially be effective materials for the treatment of soil and groundwater polluted with chlorinated benzenes. We investigated the potential intercalation of benzene sulfonate (BzS) and 1,3-benzene disulfonate (BzDS) into green rust sulfate (GR SO4 ) via ion exchange. The GR SO4 reacted with various concentrations of sulfonates were characterized by X-ray diffraction, X-ray scattering and transmission electron microscopy. GR interacted with BzDS did not result in intercalation due to stearic hindrance and electrostatic repulsion. For BzS, mixtures of GR SO4 and GR-BzS (d 001 = 14.3 Å) were obtained at molar equivalents of ion exchange capacity >5. The intercalation of BzS in the GR structure is limited (~18% intercalation) since BzS cannot fully replace SO 4 2- . The BzS molecules are likely arranged in the interlayer as a dehydrated monolayer with the -SO 3 groups facing away in alternate directions.

To date, poly(vinyl chloride) (PVC) is the most used polymer in the design of ion selective electrode (ISE) membranes. This paper is focused on the use of sulfonated poly(ether ether ketone) (SPEEK) as an alternative material to PVC for the design of ISEs. SPEEK of the desired degree of sulfonation is synthesized from poly(ether ether ketone) (PEEK). An NH4+-ISE has been chosen as a model electrode to study the efficiency of SPEEK as polymer matrix of the membrane. The material was evaluated in ionophore free ion exchanger membranes as well as in ion-selective electrodes membranes containing nonactine as ionophore. Analytical performance parameters of the prepared electrodes were evaluated. The electrodes show a slope between 50 and 60 mVdec(-1) depending on both the calibration medium and the membrane composition. A linear range of response between 10(-4) and 1.0 M and a lifetime of 1-2 months were obtained. The interferences of cations such us Ca2+, Na+, Li+ and K+ over the prepared ISEs are studied as well. Although the plasticizer in the SPEEK based membrane matrix is not necessary, its presence improves the sensibility. This makes SPEEK a good potential choice over alternative membrane matrices reported in the literature and a promising platform for the establishment of membrane components.

The mixed adsorption of the nonionic polymer poly(vinylpyrrolidone) (PVP) and the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) on kaolinite has been studied. Both components adsorb from their mixture onto the clay mineral. The overall adsorption process is sensitive to the pH, the electrolyte concentration, and the amounts of polymer and surfactant. Interpretation of the experimental data addresses also the patchwise heterogeneous nature of the clay surface. In the absence of PVP, SDBS adsorbs on kaolinite by electrostatic and hydrophobic interactions. However, when PVP is present, surfactant adsorption at 10(-2) M NaCl is mainly driven by charge compensation of the edges. The adsorption of PVP from the mixture shows similar behavior under different conditions. Three regions can be distinguished based on the changing charge of polymer-surfactant complexes in solutions with increasing SDBS concentration. At low surfactant content, PVP adsorbs by hydrogen bonding and hydrophobic interactions, whereas electrostatic interactions dominate at higher surfactant concentrations. Over the entire surfactant concentration range, polymer-surfactant aggregates are present at the edges. The composition of these surface complexes differs from that in solution and is controlled by the surface charge. (C) 2003 Elsevier Science (USA). All rights reserved.

In this paper we report a comparative study of different procedures for the inter-matrix synthesis (IMS) of monometallic Pd-Polymer-Stabilized Metal NanoParticles (PSMNPs) in sulfonated polyetherether ketone (SPEEK) as stabilizing polymeric matrix. The IMS technique consists in consecutive metal loading-reduction cycles and can be realized by using two different versions: (i) in situ and (ii) ex situ. For in situ IMS the bare polymeric material is first deposited onto the electrode surface followed by metal loading and reduction. The last step (reduction of metal ions to PSMNPs) can be done either chemically or electrochemically. Pd-PSMNPs were synthesized by varying both the Pd concentration in the loading solution and the IMS procedure. MNPs were characterized by TEM, XRD, ICP-OES and EDS techniques and the main differences found are related to MNPs size and their spatial distribution inside the polymeric matrix. The catalytic activity of Pd-PSMNPs synthesized by different versions of the IMS technique was evaluated by using PSMNPs modified electrodes as amperometric sensors.

Human lactate dehydrogenase A plays an important role in the glucose metabolism of tumor cells and constitutes an attractive target for chemotherapy. Molecular fragments able to bind in the active site of this enzyme and form hydrogen bonds with the Arg168 guanidinium group, as well as additional interactions with the loop 96-111 in the closed conformation, have been identified by virtual screening of sulfonates and experimental testing of their inhibitory effect. The sulfo group can occupy a similar position as the carboxyl group of the substrate and its structural analogs, whereas the benzothiazole group attached via a linker can be located in the coenzyme (NADH) binding site. Thus, the value of merging individual structural elements of the inhibitor by a linker was demonstrated and ways of further structural modification for the design of more effective inhibitors of lactate dehydrogenase A were established.

‘Green rust’ intercalated with aromatic sulfonates can potentially be effective materials for the treatment of soil and groundwater polluted with chlorinated benzenes. We investigated the potential intercalation of benzene sulfonate (BzS) and 1,3-benzene disulfonate (BzDS) into green rust sulfate (GRSO4) via ion exchange. The GRSO4 reacted with various concentrations of sulfonates were characterized by X-ray diffraction, X-ray scattering and transmission electron microscopy. GR interacted with BzDS did not result in intercalation due to stearic hindrance and electrostatic repulsion. For BzS, mixtures of GRSO4 and GR-BzS (d001 = 14.3 Å) were obtained at molar equivalents of ion exchange capacity >5. The intercalation of BzS in the GR structure is limited (~18% intercalation) since BzS cannot fully replace SO42-. The BzS molecules are likely arranged in the interlayer as a dehydrated monolayer with the –SO3 groups facing away in alternate directions.