1150617-04-1Relevant articles and documents
Well-controlled ATRP of 2-(2-(2-azidoethyoxy)ethoxy)ethyl methacrylate for high-density click functionalization of polymers and metallic substrates
Liu, Pingsheng,Song, Jie
, p. 1268 - 1277 (2016)
The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido-bearing methacrylate monomers (e.g., 2-(2-(2-azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 °C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well-defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number-average molecular weights (Mn) up to 22 kDa with narrow polydispersity (PDI 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface-initiated ATRP (SI-ATRP), and effectively functionalized the azide-terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well-controlled ATRP of azido-bearing methacrylates and subsequent facile high-density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications.
A bistable poly[2]catenane forms nanosuperstructures
Olson, Mark A.,Braunschweig, Adam B.,Fang, Lei,Ikeda, Taichi,Klajn, Rafal,Trabolsi, Ali,Wesson, Paul J.,Benitez, Diego,Mirkin, Chad A.,Grzybowski, Bartosz A.,Stoddart, J. Fraser
, p. 1792 - 1797 (2009)
Side-chain poly[2]catenanes at the click of a switch! A bistable side-chain poly[2]catenane has been synthesized and found to form hierarchical self-assembled hollow superstructures of nanoscale dimensions in solution. Molecular electromechanical switchin
ZWITTERIONIC POLYMERS WITH THERAPEUTIC MOIETIES
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Paragraph 0140, (2016/12/22)
The invention generally relates to zwitterionic polymers (including zwitterionic copolymers), such as polymethacrylic structures, with pendent functional moieties, such as therapeutic or biologic moieties. More particularly, the invention relates to phosphorylcholine-substituted methacrylic polymers prepared by free radical polymerization and click chemistry, for example, and compositions and products comprising same, as well as related methods and uses of the compositions, for example, as biological or therapeutic agents and in drug delivery thereof.
Thermodynamic forecasting of mechanically interlocked switches
Olson, Mark A.,Braunschweig, Adam B.,Ikeda, Taichi,Fang, Lei,Trabolsi, Ali,Slawin, Alexandra M. Z.,Khan, Saeed I.,Stoddart, J. Fraser
experimental part, p. 4391 - 4405 (2009/12/25)
Mechanically interlocked molecular (MIM) switches in the form of bistable [2]rotaxanes and [2]catenanes have proven to be - when incorporated in molecular electronic devices (MEDs) and in nanoelectromechanical systems (NEMS) - a realistic and viable alternative to the silicon chip density challenge. Structural modifications and chemical environment can have a large impact on the relaxation thermodynamics of the molecular motions, such as translation and circumrotation in bistable rotaxanes and catenanes responsible for the operation of devices based on MIMs. The effects of structural modifications on the difference in free energy (ΔGo) for the equilibrium processes in switchable MIMs can be predicted by considering, firstly, the interactions present in their precursor pseudorotaxanes. By employing isothermal titration microcalorimetry (ITC) to investigate the thermodynamic parameters governing pseudorotaxane formation for a series of monosubstituted, acceptor host cyclophanes with various donor guests, in conjunction with X-ray crystallographic data, an obvious link between the noncovalent bonding interactions in pseudorotaxanes and MIMs that survive following the formation of the mechanical bond can be identified. It follows that the changes (ΔΔGo values) in the difference of free energy during the formation of different pseudorotaxanes can subsequently be extrapolated to predict ΔGo values for the thermodynamics associated with switching in analogous MIM switches, employing the same donor-acceptor recognition components. In this manner, a systematic and predictive thermodynamic approach to designing and tuning switchable MIMs and MIM-based materials has been established. Additionally, these thermodynamic relationships are reminiscent of the long forgotten concept of the 'parachor' as a molecular descriptor with respect to the additivity of physical properties in chemical systems dealing specifically with quantitative structure property-activity relationships (QSPR/QSAR).
