Cyclolinear polysiloxanes. I. Synthesis and characterization

The synthesis and characterization of two novel cyclic siloxanes, diacetoxydiethyltetramethylcyclotetrasiloxane and diacetoxytriethylpentamethylcyclopentasiloxane, and cyclolinear polymers synthesized from these monomers are presented. The cyclic siloxanes were synthesized from tetramethylcyclotetrasiloxane and pentamethylcyclopentasiloxane, respectively, by acetylation followed by ethylation. The cyclic monomers were characterized with ¹H NMR spectroscopy. Subsequently, the cyclic siloxanes were self‐condensed into cyclolinear polysiloxanes and cocondensed (extended) with silanol‐terminated polydimethylsiloxane into high‐molecular‐weight polymers containing cyclic units withlinearpolydimethylsiloxane spacers (extended cyclolinear polysiloxanes). The molecular weights of both the cyclolinear polysiloxanes and extended cyclolinear polysiloxanes were determined. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4039?4052, 2006     

Click chemistry in materials synthesis. II. Acid‐swellable crosslinked polymers made by copper‐catalyzed azide–alkyne cycloaddition

A highly crosslinked hyperbranched polymer that rapidly swells and shrinks in a halogenated solvent in response to the addition of an acid or base has been prepared by Cu(I) catalysis of the reaction between a diazide and an amine‐containing trialkyne. The triazole linkages in the polymer are highly stable and may also play a role in the swelling behavior. The swelling–deswelling process is reversible. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5513–5518, 2006     

Anion Responsive Imidazolium‐Based Polymers

Stimuli responsiveness in polymer design is providing basis for diversely new and advanced materials that exhibit switchable porosity in membranes and coatings, switchable particle formation and thermodynamically stable nanoparticle dispersions, polymers that provide directed mechanical stress in response to intensive fields, and switchable compatibility of nanomaterials in changing environments. The incorporation of ionic liquid monomers has resulted in many new polymers based on the imidazolium group. These polymers exhibit all of the above‐articulated material properties. Some insight into how these anion responsive polymers function has become empirically available. Much opportunity remains for extending our understanding as well as for designing more refined stimuli‐responsive materials.     

A reduction sensitive cascade biodegradable linear polymer

Cascade degradable linear polymers offer the potential for a high degree of control over the degradation process. They comprise a backbone that is stable in the presence of an end cap, but upon removal of the end cap a cascade of intramolecular reactions is initiated that leads of depolymerization of the polymer backbone. Reported here is a new polymer backbone based on N,N′‐dimethylethylenediamine and 2‐mercaptoethanol linked by carbamates and thiocarbamates. A disulfide end cap was incorporated such that its cleavage under reducing conditions revealed the thiol of 2‐mercaptoethanol, leading to alternating cyclizations of the 2‐mercaptoethanol and N,N′‐dimethylethylenediamine moieties to provide 1,3‐oxathiolan‐2‐one and N,N′‐dimethylimidazolidinone, respectively. The degradation was monitored by ¹H NMR and GPC. The expected products were observed, along with a portion of nondegradable polymer that was likely cyclic species. Overall, the results demonstrate the promise of this new class of polymers to degrade selectively in reducing environments such as hypoxic tumor tissue or the intracellular compartments of cells. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3977–3985, 2010     

Stimuli‐responsive polymers in the 21st century: Elaborated architecture to achieve high sensitivity,fast response,and robust behavior

Life is polymeric in its essence. The living cell contains a range of biopolymers such as proteins, carbohydrates, and nucleic acids. The cells are often compartmentalized via membranes that are composed of lipids. These are small molecules, but they spontaneously aggregate into supermolecular structures. The building blocks of these lipids are among others fatty acids, structures built from methylene oligomers. Biopolymers are sensitive to external stimuli. There are examples where the molecules show a highly non‐linear response to external stimuli. This is seen as moderate changes in structural properties in response to changes in an external parameter until a critical point is reached where a dramatic change in molecular properties takes place upon an incremental change in the external conditions. After the transition, the system responds poorly to further changes. Such non‐linear responses contribute to dramatic cooperative conformational changes leading to strong effects in the biological system. The strong response is an integrated effect of many weak interactions, and it is the cooperativity between all these interactions that are the driving forces for processes occurring in such systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Stimuli‐responsive polymers. VIII. Polyesters and poly(ester amides) containing azobenzene and chiral binaphthylene segments: Highly adaptive materials endowed with light‐, heat‐, and solvent‐regulated optical rotatory power

Azobenzene‐modified polyesters and poly(ester amide)s fitted with chiral, atropisomeric binaphthylene segments were prepared by a series of low‐temperature polycondensation reactions carried out in polar solvent media. When compared with their polyaramide counterparts studied earlier, these materials had significantly improved solubility behaviors and were readily dissolved by a wide range of organic solvents. In solution, each of these constructs underwent photoinduced oscillations in optical rotatory power when subjected to multiple UV‐light/visible‐light illumination cycles that drove trans?cis isomerization reactions along their polymer chains. Light‐regulated chiroptical perturbations were dependent on polymer backbone structures and were further modulated by well‐coordinated temperature fluctuations and by the nature of the solvent medium employed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 207–218, 2006     

Energy transfer from fluorene‐based conjugated polyelectrolytes to on‐chain and self‐assembled porphyrin units

A new water soluble fluorene‐based polyelectrolyte containing on‐chain porphyrin units has been synthesized via Suzuki coupling, for use in optoelectronic devices. The material consist of a random copolymer of poly{1,4‐phenylene‐[9,9‐bis(4‐phenoxy butylsulfonate)]fluorene‐2,7‐diyl} (PBS‐PFP) and a 5,15‐diphenylporphyrin (DPP). The energy transfer process between the PBS‐PFP units and the porphyrin has been investigated through steady state and time‐resolved measurements. The copolymer PBS‐PFP‐DPP displays two different emissions one located in the blue region of the spectra, corresponding to the fluorene part and another in the red due to fluorescent DPP units either formed directly or by exciton transfer. However, relatively inefficient energy transfer from the PFP to the on‐chain porphyrin units was observed. We compare this with a system involving an anionic blue light‐emitting donor PBS‐PFP and a anionic red light‐emitting energy acceptor meso‐tetrakisphenylporphyrinsulfonate (TPPS), self‐assembled by electrostatic attraction induced by Ca²⁺. Based on previous studies related to chain aggregation of the anionic copolymer PBS‐PFP, two different solvent media were chosen to further explore the possibilities of the self‐assembled system: dioxane–water and aqueous nonionic surfactant n‐dodecylpentaoxyethylene glycol ether (C₁₂E₅). In contrast, with the on‐chain PBS‐PFP‐DPP system the strong overlap of the 0‐0 emission peak of the PBS‐PFP and the Soret absorption band of the TPPS results in an efficient Förster transfer. This is strongly dependent on the solvent medium used. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

2,6‐Diaminopyridine and Acrylamide‐Based Copolymers with Upper Critical Solution Temperature‐type Behavior in Aqueous Solution

A novel copolymer based on supramolecular motif 2,6‐diaminopyridine and water‐soluble acrylamide, poly[N‐(6‐acetamidopyridin‐2‐yl) acrylamide‐co‐acrylamide], was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization with various monomer compositions. The thermoresponsive behavior of the copolymers was studied by turbidimetry and dynamic light scattering (DLS). The obtained copolymers showed an upper critical solution temperature (UCST)‐type phase transition behavior in water and electrolyte solution. The phase transition temperature was found to increase with decreasing amount of acrylamide in the copolymer and increasing concentration of the solution. Furthermore, the phase transition temperature varied in aqueous solutions of electrolytes according to the nature and concentration of the electrolyte in accordance with the Hoffmeister series. A dramatic solvent isotope effect on the transition temperature was observed in this study, as the transition temperature was almost 10–12 °C higher in D₂O than in H₂O at the same concentration and acrylamide composition. The size of the aggregates below the transition temperature was larger in D₂O compared to that in H₂O that can be explained by deuterium isotope effect. The thermoresponsive behavior of the copolymers was also investigated in different cell medium and found to be exhibited UCST‐type phase transition behavior in different cell medium. Such behavior of the copolymers can be useful in many applications including biomedical, microfluidics, optical materials, and in drug delivery. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2064–2073     

Synthesis,Characterization, and thermoresponsive properties of Helical Polypeptides Derivatized from Poly(γ−4‐(3‐chloropropoxycarbonyl)benzyl‐L‐glutamate)

A series of side‐chain‐functionalized α‐helical polypeptides, i.e., poly(γ‐4‐(3‐chloropropoxycarbonyl)benzyl‐_L‐glutamate) (6) have been prepared from n‐butylamine initiated ring‐opening polymerization (ROP) of γ‐4‐(3‐chloropropoxycarbonyl)benzyl‐_L‐glutamic acid‐based N‐carboxyanhydride. Polypeptides bearing oligo‐ethylene‐glycol (OEG) groups or 1‐butylimidazolium salts were prepared from 6 via copper‐mediated [2+3] alkyne‐azide 1,3‐dipolar cycloaddition or nuleophilic substitution, respectively. CD and FTIR analysis revealed that the polymers adopt α‐helical conformations both in solution and the solid state. Polymers bearing OEG (m = 3) side‐chains showed reversible LCST‐type phase transition behaviors in water while polymers bearing 1‐butylimidazolium and I^? counter‐anions exhibited reversible UCST‐type transitions in water. Variable‐temperature UV‐vis analysis revealed that the phase transition temperatures (T_pts) were dependent on the main‐chain length and polymeric concentration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2469–2480     

Nanotechnology with soft materials.

Nature exploits self-organization of soft materials in many ways, to produce cell membranes, biopolymer fibers and viruses, to name just three. Mankind is now able to design materials at the nanoscale, whether through atom-by-atom or molecule-by-molecule methods (top-down) or through self-organization (bottom-up). The latter method encompasses soft nanotechnology. Self-organization of soft materials can be exploited to create a panoply of nanostructures for diverse applications. The richness of structures results from the weak ordering because of noncovalent interactions. Thus, thermal energy is important as it enables transitions between phases with differing degrees of order. The power of self-organization may be harnessed most usefully in a number of nanotechnology applications, which include the preparation of nanoparticles, the templating of nanostructures, nanomotor design, the exploitation of biomineralization, and the development of functionalized delivery vectors.     

Synthesis and properties of fluorene‐based polyheteroarylenes for photovoltaic devices

Novel copolymers consisting of the alternating push–pull comonomers fluorene and thieno[3,4‐b]pyrazine/quinoxaline were synthesized by a palladium‐catalyzed Suzuki cross‐coupling reaction in 60–80% yields. The structure of the deeply colored copolymers was confirmed with ¹H and ¹³C NMR. All the new materials were characterized with spectroscopic and electrochemical methods. Bulk heterojunction organic solar cells based on some of the novel polymers in combination with the well‐known fullerene acceptor [6,6]‐phenyl C₆₁–butyric acid methyl ester were fabricated, and their photovoltaic parameters were measured. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6952–6961, 2006     

Linear poly(amide triazole)s derived from d‐glucose

The click reaction between azides and alkynes is been increasingly employed in the preparation of polymers. In this article, we describe the synthesis and click polyaddition reaction of a new A‐B‐type amide monomer—prepared from d ‐glucose as renewable resource—containing the alkyne and azide functions. Both Cu(I)‐catalyzed and metal‐free click polymerization methods were used to prepare glucose‐derived poly(amide triazole)s. The resulting polymers had weight‐average molecular weights in the 45,000–129,000 range and were characterized by GPC, IR, and NMR spectroscopies. Thermal and X‐ray diffraction studies revealed them to be amorphous. Their qualitative solubilities in various solvents and their water sorption have been studied. The poly(amide triazole)s having the alcohol functions protected as methyl ether were water‐soluble. The presence of the amide functions along the polymer chain made these polytriazoles degradable in the presence of sodium deuteroxide. The degradation was monitored by NMR analysis, and the degradation product was characterized by HRMS. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 629–638     

Poly(ProDOT‐Et2): A High‐Contrast,High‐Coloration Efficiency Electrochromic Polymer

The synthesis and electrochemical polymerization of 3,3‐diethyl‐3,4‐dihydro‐2H‐thieno‐[3,4‐b][1,4]dioxepine (ProDOT‐Et₂) was performed resulting in a stable electrochromic polymer capable of switching between an absorbing blue neutral state and a highly transmissive sky‐blue oxidized state in sub‐second time frames. High optical switching contrast ratios (up to 75% at λ_max) and high composite coloration efficiencies (505 cm²/C) were measured.