Synthesis, characterization, and ion-complexing properties of polymers displaying densely packed arrays of crown-ethers as lateral substituents

Liu, Ming; Peyrat, Sandrine; Illy, Nicolas; Wintgens, Véronique; Brissault, Blandine; Penelle, Jacques; Barbier, Valessa

doi:10.1002/pola.27245

Cited by 3 publications

(8 citation statements)

References 27 publications

(36 reference statements)

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“…It is possible, however, that some preliminary drying is needed in the case of monomers bearing hydrophilic moie ties on the esters such as PEG or crown ethers, as suggested before. [11] In some cases (typically when targeting high degrees of polymerization or when attempting to scale up), a small shoulder could be identified in the SEC chromatogram, although not systematically. Experiments specifically designed to amplify the issue indicated that the impurity is a polycyclo propane as well, with a degree of polymerization of about 3/4th the degree of polymerization of the main polymer.…”

Section: Discussionmentioning

confidence: 99%

“…It should be mentioned that, using the above procedure, no prior drying of the monomer is required, despite its polar character. It is possible, however, that some preliminary drying is needed in the case of monomers bearing hydrophilic moieties on the esters such as PEG or crown ethers, as suggested before …”

Section: Discussionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] The ringopening polymeri zation of cyclopropanes was not a new concept at the time we started investigating the issue, but previous attempts had always led to oligomers, with broad to very broad molecular weight dis tributions. [14] For the first time, with the advent of our activated monomer approach, efficient procedures to polymerize livingly threemembered ring carbon monomers became available, yielding carbonchain polymers substituted on every third atom alongside the backbone (see Scheme 1A for an example).…”

Section: Introductionmentioning

confidence: 99%

“…Over the past two decades, our group has been describing the living anionic polymerization of activated cyclopropanes in about fifteen research papers . The ring‐opening polymerization of cyclopropanes was not a new concept at the time we started investigating the issue, but previous attempts had always led to oligomers, with broad to very broad molecular weight distributions .…”

Section: Introductionmentioning

confidence: 99%

“…Using one of the above two reactions conditions (or both in a few cases), a large variety of entirely novel functional polymers has been obtained in our laboratory, with either simple alkyl groups on the esters or more complex lateral substituents such as crown ethers or cholesteric mesogens . Many collaborators, from undergraduate students to senior scientists, have successfully been trained with the required procedures, and have in the vast majority of cases been able to effectively achieve the targeted living polymerizations.…”

Section: Introductionmentioning

confidence: 99%

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Design of Optimized Reaction Conditions for the Efficient Living Anionic Polymerization of Cyclopropane‐1,1‐Dicarboxylates

Benlahouès

Brissault

Boileau

et al. 2017

Macro Chemistry & Physics

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was also offered, opening an access route to a large family of laterally functionalized poly mers (for example, poly(1) in Scheme 1). In addition, high temperatures, up to 120-140 °C, can be used and further modi fications of the obtained macrocarbanion with electrophiles are possible due to the excellent thermal stability and wellknown nucleophilicity of malonate carbanions, the propagating species involved in these polymerizations. [3,7,14] The prototypical monomers that have been efficiently polymerized thus far in this series of activated cyclopropanes are based on cyclopropyl rings 1 geminally substituted by two electronwithdrawing groups, typically esters (Scheme 1) but also nitriles. Monomers with two propyl ester groups (either as n or ipropyl) have been particularly investigated, as both the monomers and their homopolymers are soluble in a wide variety of solvents, in contrast to methyl or ethyl ester polymers whose solubility in organic solvents com patible with mandatory anionic polymerization conditions is low, due to their high susceptibility to crystallize.Conditions that have so far been found to polymerize 1 liv ingly can be schematically divided into two sets, depending on the type of counterion associated to the malonate RC(COOR) − carbanion on the growing chain. One set involves simple alkali ions, [1][2][3][4] while the other one implicates the large tBuP 4 H + phosphazenium cation derived from the protonation of tBuP 4 superbase (see Scheme 3 for a mechanism). [6,7] Both systems have their pros and cons. The first one is much cheaper, involves relatively straightforward workup processes, but the polymerization is slow, has to be carried out at high tempera tures (typically over 100 °C), which are not necessarily compat ible with some functional groups on the ester, and is practi cally limited to degrees of polymerization of 20-30. The second one is much faster, with polymerization temperatures usually close to 50-60 °C. As a result, it tolerates a wide variety of ini tiators and functional groups on the monomers, and much higher degrees of polymerization can be targeted. In addition, polymerizations can be carried out in classical solvents such as THF or toluene. The main drawbacks are the high cost of the required, commercially available, tBuP 4 superbase, and the lipophilicity and possible toxicity of the generated tBuP 4 H + phosphazenium ion, [15,16] which can seriously complicate the purification of the obtained polymers/oligomers. Cyclopropane PolymerizationA reinvestigation of the experimental parameters used when polymerizing anionically a cyclopropane-1,1-dicarboxylate indicates that several key steps have to be considered, but that other steps-including some routinely used up to now-although not harmful, are nevertheless useless. A robust protocol is thus designed whose implementation allows us to routinely control the polymerization of di-n-propyl cyclopropane-1,1-dicarboxylate, used as a model monomer for the entire family of cyclopropyl monomers geminally activated by two est...

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Design of Optimized Reaction Conditions for the Efficient Living Anionic Polymerization of Cyclopropane‐1,1‐Dicarboxylates

Benlahouès

Brissault

Boileau

et al. 2017

Macro Chemistry & Physics

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Synthesis of new Azo‐based liquid crystalline polymers and their selective sensing behaviors to alkali metal ions

Byun

Lee

Han

2016

J. Polym. Sci. Part A: Polym. Chem.

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We report novel liquid crystalline (LC) polymers containing pendant azobenzene moieties with n-dodecyl substituents and ethyleneoxy spacers of different lengths and describe their selective detection behaviors to alkali metal ions. The new azopolymers produce homogenous smectic phases with a typical fan-shaped texture. UV-Vis and 1 H NMR studies confirm that the azopolymers selectively bind to Li 1 and Na 1 , but do not complex with K 1 , Ba 21 , Mg 21 , or Ca 21 . Both the ethyleneoxy spacer and azobenzene units participate in binding to Li 1 and Na 1 cations in solution. Interestingly, after formation of the complexed structure, the ratio of cis to trans con-former is considerably increased suggesting stronger interactions of the cis conformer with alkali metal ions. Irradiation of the complexed structure with 365 nm UV induces conversion of the uncomplexed trans to the cis. These findings suggest a great potential of the LC azopolymers as selective sensors or separation membranes for alkali metal ions.

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Metal-Chelating Polymers by Anionic Ring-Opening Polymerization and Their Use in Quantitative Mass Cytometry

et al. 2012

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Metal-chelating polymers (MCPs) are important reagents for multiplexed immunoassays based on mass cytometry. The role of the polymer is to carry multiple copies of individual metal isotopes, typically as lanthanide ions, and to provide a reactive functionality for convenient attachment to a monoclonal antibody (mAb). For this application, the optimum combination of chain length, backbone structure, end group, pendant groups, and synthesis strategy has yet to be determined. Here we describe the synthesis of a new type of MCP based on anionic ring-opening polymerization of an activated cyclopropane (the diallyl ester of 1,1-cyclopropane dicarboxylic acid) using a combination of 2-furanmethanethiol and a phosphazene base as the initiator. This reaction takes place with rigorous control over molecular weight, yielding a polymer with a narrow molecular weight distribution, reactive pendant groups for introducing a metal chelator, and a functional end group with orthogonal reactivity for attaching the polymer to the mAbs. Following the ring-opening polymerization, a two-step transformation introduced diethylenetriaminepentaacetic acid (DTPA) chelating groups on each pendant group. The polymers were characterized by NMR, size exclusion chromatography (SEC), and thermogravimetric analysis (TGA). The binding properties toward Gd3+ as a prototypical lanthanide (Ln) ion were also studied by isothermal titration calorimetry (ITC). Attachment to a mAb involves a Diels–Alder reaction of the terminal furan with a bismaleimide, followed by a Michael addition of a thiol on the mAb, generated by mild reduction of a disulfide bond in the hinge region. Polymer samples with a number average degree of polymerization of 35, with a binding capacity of 49.5 ± 6 Ln3+ ions per chain, were loaded with 10 different types of Ln ions and conjugated to 10 different mAbs. A suite of metal-tagged Abs was tested by mass cytometry in a 10-plex single cell analysis of human adult peripheral blood, allowing us to quantify the antibody binding capacity of 10 different cell surface antigens associated with specific cell types.

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Synthesis, characterization, and ion-complexing properties of polymers displaying densely packed arrays of crown-ethers as lateral substituents

Cited by 3 publications

References 27 publications

Design of Optimized Reaction Conditions for the Efficient Living Anionic Polymerization of Cyclopropane‐1,1‐Dicarboxylates

Design of Optimized Reaction Conditions for the Efficient Living Anionic Polymerization of Cyclopropane‐1,1‐Dicarboxylates

Synthesis of new Azo‐based liquid crystalline polymers and their selective sensing behaviors to alkali metal ions

Metal-Chelating Polymers by Anionic Ring-Opening Polymerization and Their Use in Quantitative Mass Cytometry

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