-
Macromolecular Rapid Communications Jul 2018The fabrication of polymer brushes via surface-initiated controlled radical polymerizations has progressively developed beyond a simple surface functionalization... (Review)
Review
The fabrication of polymer brushes via surface-initiated controlled radical polymerizations has progressively developed beyond a simple surface functionalization technique, enabling the design of complex polymer interfaces with a quasi-3D molecular organization. The modulation of polymer brush structure has led to an extremely broad tuning potential for technologically relevant interfacial, physicochemical properties, allowing one to precisely tune swelling, nanomechanical, and nanotribological characteristics of polymer films. In addition, the synthesis of multilayer brush interfaces with hierarchical architecture has been exploited to control biological phenomena on modified platforms, such as cell adhesion and settlement, or to fully prevent biological contamination from bacteria. In this feature article, the most recent developments in the synthesis and application of quasi-3D structured polymer brushes are summarized, placing particular attention on how the tuning of grafted-polymer architecture could translate into a variation of interfacial characteristics.
Topics: Acrylic Resins; Cell Adhesion; Molecular Conformation; Polymerization; Polymers; Surface Properties
PubMed: 29786905
DOI: 10.1002/marc.201800189 -
Current Drug Metabolism 2018Ternary solid dispersions have been demonstrated to be an effective strategy in the improvement of drug absorption and bioavailability. (Review)
Review
BACKGROUND
Ternary solid dispersions have been demonstrated to be an effective strategy in the improvement of drug absorption and bioavailability.
METHOD
The applications of the combination of hydrophilic polymers with the potential of hydrophobic polymer incorporation at moderate concentrations have been discussed in recent publications.
RESULTS
In this paper, the general review of this specific type of solid dispersion will be provided with comprehensive understanding of polymer blends of either hydrophilic or hydrophobic polymers. A detailed description of miscible polymers has been developed in recent studies. In addition to dissolution rate improvement, the role of second polymers in crystal growth inhibition and in maintaining the amorphous state will be mentioned.
CONCLUSION
We also present a summary of characterization techniques commonly used to evaluate solid dispersion and polymer miscibility.
Topics: Biological Availability; Drug Design; Hydrophobic and Hydrophilic Interactions; Pharmaceutical Preparations; Polymers
PubMed: 29956619
DOI: 10.2174/1389200219666180628171100 -
Accounts of Chemical Research May 2015Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes... (Review)
Review
Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes started to give access to a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. A few years later, the concept of click chemistry revolutionized the way polymer chemists approached synthetic routes. Among the few reactions that could qualify as click, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) initially stood out. Soon, many old and new reactions, including cycloadditions, would further enrich the synthetic macromolecular chemistry toolbox. Whether click or not, cycloadditions are in any case powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes, responsiveness. Here, we wish to describe cycloaddition methodologies that have been reported in the last 10 years in the context of macromolecular engineering, with a focus on those developed in our laboratories. The overarching structure of this Account is based on the three most commonly encountered cycloaddition subclasses in organic and macromolecular chemistry: 1,3-dipolar cycloadditions, (hetero-)Diels-Alder cycloadditions ((H)DAC), and [2+2] cycloadditions. Our goal is to briefly describe the relevant reaction conditions, the advantages and disadvantages, and the realized polymer applications. Furthermore, the orthogonality of most of these reactions is highlighted because it has proven highly beneficial for generating unique, multifunctional polymers in a one-pot reaction. The overview on 1,3-dipolar cycloadditions is mostly centered on the application of CuAAC as the most travelled route, by far. Besides illustrating the capacity of CuAAC to generate complex polymeric architectures, alternative 1,3-dipolar cycloadditions operating without the need for a catalyst are described. In the area of (H)DA cycloadditions, beyond the popular maleimide/furan couple, we present chemistries based on more reactive species, such as cyclopentadienyl or thiocarbonylthio moieties, particularly stressing the reversibility of these systems. In these two greater families, as well as in the last section on [2+2] cycloadditions, we highlight phototriggered chemistries as a powerful tool for spatially and temporally controlled materials synthesis. Clearly, cycloaddition chemistry already has and will continue to transform the field of polymer chemistry in the years to come. Applying this chemistry enables better control over polymer composition, the development of more complicated polymer architectures, the simplification of polymer library production, and the discovery of novel applications for all of these new polymers.
Topics: Cyclization; Molecular Structure; Polymers
PubMed: 25871918
DOI: 10.1021/acs.accounts.5b00075 -
Emerging Topics in Life Sciences Dec 2022Biology demonstrates meticulous ways to control biomaterials self-assemble into ordered and disordered structures to carry out necessary bioprocesses. Empowering the... (Review)
Review
Biology demonstrates meticulous ways to control biomaterials self-assemble into ordered and disordered structures to carry out necessary bioprocesses. Empowering the synthetic polymers to self-assemble like biomaterials is a hallmark of polymer physics studies. Unlike protein engineering, polymer science demystifies self-assembly by purposely embedding particular functional groups into the backbone of the polymer while isolating others. The polymer field has now entered an era of advancing materials design by mimicking nature to a very large extend. For example, we can make sequence-specific polymers to study highly ordered mesostructures similar to studying proteins, and use charged polymers to study liquid-liquid phase separation as in membraneless organelles. This mini-review summarizes recent advances in studying self-assembly using bio-inspired strategies on single-component and multi-component systems. Sequence-defined techniques are used to make on-demand hybrid materials to isolate the effects of chirality and chemistry in synthetic block copolymer self-assembly. In the meantime, sequence patterning leads to more hierarchical assemblies comprised of only hydrophobic and hydrophilic comonomers. The second half of the review discusses complex coacervates formed as a result of the associative charge interactions of oppositely charged polyelectrolytes. The tunable phase behavior and viscoelasticity are unique in studying liquid macrophase separation because the slow polymer relaxation comes primarily from charge interactions. Studies of bio-inspired polymer self-assembly significantly impact how we optimize user-defined materials on a molecular level.
Topics: Polymers; Proteins; Polyelectrolytes; Hydrophobic and Hydrophilic Interactions; Biocompatible Materials
PubMed: 36254846
DOI: 10.1042/ETLS20220057 -
Molecules (Basel, Switzerland) Sep 2022A new programed upper critical solution temperature-type thermoresponsive polymer was developed using water-soluble anionic polymer conjugates derived from...
A new programed upper critical solution temperature-type thermoresponsive polymer was developed using water-soluble anionic polymer conjugates derived from polyallylamine and phthalic acid with cleavage-induced phase transition property. Intrinsic charge inversion from anion to cation of the polymer side chain is induced through a side chain cleavage reaction in acidic aqueous media. With the progress of side chain cleavage under fixed external conditions, the polymer conjugates express a thermoresponsive property, followed by shifting a phase boundary due to the change in polymer composition. When the phase transition boundary eventually reached the examined temperature, phase transition occurs under fixed external conditions. Such new insight obtained in this study opens up the new concept of time-programed stimuli-responsive polymer possessing a cleavage-induced phase transition.
Topics: Anions; Phase Transition; Polymers; Stimuli Responsive Polymers; Temperature; Water
PubMed: 36144815
DOI: 10.3390/molecules27186082 -
Bioconjugate Chemistry Mar 2017As potent and selective therapeutic agents, peptides and proteins are an important class of drugs, but they typically have suboptimal pharmacokinetic profiles. One... (Review)
Review
As potent and selective therapeutic agents, peptides and proteins are an important class of drugs, but they typically have suboptimal pharmacokinetic profiles. One approach to solve this problem is their conjugation with "stealth" polymers. Conventional methods for conjugation of this class of polymers to peptides and proteins are typically carried out by reactions that have poor yield and provide limited control over the site of conjugation and the stoichiometry of the conjugate. To address these limitations, new chemical and biological approaches have been developed that provide new molecular tools in the bioconjugation toolbox to create stealth polymer conjugates of peptides and proteins with exquisite control over their properties. This review article highlights these recent advances in the synthesis of therapeutic peptide- and protein-stealth polymer conjugates.
Topics: Animals; Chemistry Techniques, Synthetic; Humans; Models, Molecular; Peptides; Polymers; Proteins
PubMed: 27998056
DOI: 10.1021/acs.bioconjchem.6b00652 -
Advanced Healthcare Materials Mar 2019Block copolymers with unique architectures and those that can self-assemble into supramolecular structures are used in medicine as biomaterial scaffolds and delivery... (Review)
Review
Block copolymers with unique architectures and those that can self-assemble into supramolecular structures are used in medicine as biomaterial scaffolds and delivery vehicles for cells, therapeutics, and imaging agents. To date, much of the work relies on controlling polymer behavior by varying the monomer side chains to add functionality and tune hydrophobicity. Although varying the side chains is an efficient strategy to control polymer behavior, changing the polymer backbone can also be a powerful approach to modulate polymer self-assembly, rigidity, reactivity, and biodegradability for biomedical applications. There are many developments in the syntheses of polymers with segmented backbones, but these developments are not widely adopted as strategies to address the unique constraints and requirements of polymers for biomedical applications. This review highlights dual polymerization strategies for the synthesis of backbone-segmented block copolymers to facilitate their adoption for biomedical applications.
Topics: Biocompatible Materials; Free Radicals; Polymerization; Polymers
PubMed: 30369103
DOI: 10.1002/adhm.201800861 -
ACS Applied Materials & Interfaces Jan 2019Polydiacetylenes are a class of conjugated polymers exhibiting unique color and fluorescence properties and employed as useful sensing vehicles. Here we demonstrate for...
Polydiacetylenes are a class of conjugated polymers exhibiting unique color and fluorescence properties and employed as useful sensing vehicles. Here we demonstrate for the first time that the dielectric properties of polydiacetylenes can be exploited for vapor sensing. Specifically, electrodes coated with polydiacetylenes, embedded within a porous polyvinylpyrrolidone (PVP) matrix, exhibit significant capacitance transformations upon exposure to different vapors. The capacitive response of the polydiacetylene/PVP films depended upon both the structures of the diacetylene monomer and the extent of ultraviolet irradiation (i.e., polymerization), underscoring a unique sensing mechanism affected by conjugation, structure, and dielectric properties of the polydiacetylene/polymer matrix. Importantly, the variability of polydiacetylene structures allows vapor identification through an array-based pattern recognition (i.e., artificial nose). This study opens new avenues for applications of polydiacetylene systems, particularly pointing to their dielectric properties as powerful sensing determinants.
Topics: Electronic Nose; Polyacetylene Polymer; Polymers; Povidone
PubMed: 30608135
DOI: 10.1021/acsami.8b20930 -
Journal of Controlled Release :... Dec 2015Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of... (Review)
Review
Sugar-based polymers have been extensively explored as a means to increase drug delivery systems' biocompatibility and biodegradation. Here,we review he use of sugar-based polymers for drug delivery applications, with a particular focus on the utility of the sugar component(s) to provide benefits for drug targeting and stimuli responsive systems. Specifically, numerous synthetic methods have been developed to reliably modify naturally-occurring polysaccharides, conjugate sugar moieties to synthetic polymer scaffolds to generate glycopolymers, and utilize sugars as a multifunctional building block to develop sugar-linked polymers. The design of sugar-based polymer systems has tremendous implications on both the physiological and biological properties imparted by the saccharide units and are unique from synthetic polymers. These features include the ability of glycopolymers to preferentially target various cell types and tissues through receptor interactions, exhibit bioadhesion for prolonged residence time, and be rapidly recognized and internalized by cancer cells. Also discussed are the distinct stimuli-sensitive properties of saccharide-modified polymers to mediate drug release under desired conditions. Saccharide-based systems with inherent pH- and temperature-sensitive properties, as well as enzyme-cleavable polysaccharides for targeted bioactive delivery, are covered. Overall, this work emphasizes inherent benefits of sugar-containing polymer systems for bioactive delivery.
Topics: Animals; Carbohydrates; Drug Delivery Systems; Humans; Polymers
PubMed: 26423239
DOI: 10.1016/j.jconrel.2015.09.053 -
ChemPlusChem May 2022The chiral self-assembly of polymers in dispersions plays an important role in chiral chemistry and self-assembly. In general, both polymerization-induced self-assembly... (Review)
Review
The chiral self-assembly of polymers in dispersions plays an important role in chiral chemistry and self-assembly. In general, both polymerization-induced self-assembly (PISA) and post-polymerization self-assembly can be used to prepare polymer nanoassemblies. In chirality induction or transfer processes, the self-assembly manner of the polymers greatly affects the chiral expression of the nanostructure and cannot be ignored in the chiral fields. Moreover, unique chiral expression and morphological transition of polymer assemblies in dispersions enable the preparation of advanced functional chiroptical materials. Herein, this Review discusses recent advances in chiral expression and morphology control in polymer dispersion systems, particularly the comparison between traditional post-polymerization self-assembly and in situ PISA strategies, to predict and advance chirality control in polymers.
Topics: Nanostructures; Polymerization; Polymers
PubMed: 35182052
DOI: 10.1002/cplu.202100556