Modified Polymer Surfaces: Thin Films of Silicate Composites via Polycaprolactone Melt Fusion.

Polymer/layered silicate composites have gained huge attention in terms of research and industrial applications. Traditional nanocomposites contain particles regularly dispersed in a polymer matrix. In this work, a strategy for the formation of a composite thin film on the surface of a polycaprolactone (PCL) matrix was developed. In addition to the polymer, the composite layer was composed of the particles of saponite (Sap) modified with alkylammonium cations and functionalized with methylene blue. The connection between the phases of modified Sap and polymer was achieved by fusing the chains of molten polymer into the Sap film. The thickness of the film of several µm was confirmed using electron microscopy and X-ray tomography. Surfaces of precursors and composite materials were analyzed in terms of structure, composition, and surface properties. The penetration of polymer chains into the silicate, thus joining the phases, was confirmed by chemometric analysis of spectral data and changes in some properties upon PCL melting. Ultimately, this study was devoted to the spectral properties and photoactivity of methylene blue present in the ternary composite films. The results provide directions for future research aimed at the development of composite materials with photosensitizing, photodisinfection, and antimicrobial surfaces.

Combined Therapy with Simvastatin- and Coenzyme-Q10-Loaded Nanoparticles Upregulates the Akt-eNOS Pathway in Experimental Metabolic Syndrome.

In addition to their LDL-cholesterol-lowering effect, statins have pleiotropic beneficial effects on the cardiovascular system. However, long-term treatment with statins may be associated with serious side effects. With the aim to make statin therapy more effective, we studied the effects of simvastatin- and coenzyme-Q10-loaded polymeric nanoparticles on the lipid profile and nitric oxide (NO)/reactive oxygen species (ROS) balance in the heart and aorta of adult male obese Zucker rats. The rats were divided into an untreated group, a group treated with empty nanoparticles, and groups treated with simvastatin-, coenzyme Q10 (CoQ10)-, or a combination of simvastatin- and CoQ10-loaded nanoparticles (SIMV+CoQ10). After 6 weeks, the lipid profile in the plasma and the concentration of conjugated dienes in the liver were determined. Nitric oxide synthase (NOS) activity, Akt, endothelial NOS (eNOS), phosphorylated eNOS (p-eNOS), nicotinamide adenine dinucleotide phosphate (NADPH) oxidase, and nuclear factor kappaB (NF-kappaB) protein expressions were measured in the heart and aorta. All simvastatin, CoQ10, and SIMV+CoQ10 treatments decreased plasma LDL levels, but only the combined SIMV+CoQ10 treatment increased NOS activity and the expression of Akt, eNOS, and p-eNOS in both the heart and the aorta. Interestingly, NADPH oxidase in the heart and NF-kappaB protein expression in the aorta were decreased by all treatments, including nanoparticles alone. In conclusion, only combined therapy with SIMV- and CoQ10-loaded nanoparticles increased NOS activity and upregulated the Akt-eNOS pathway in obese Zucker rats, which may represent a promising tool for the treatment of cardiometabolic diseases.

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers.

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.

Properties and Degradation of Novel Fully Biodegradable PLA/PHB Blends Filled with Keratin.

The utilization of keratin waste in new materials formulations can prevent its environmental disposal problem. Here, novel composites based on biodegradable blends consisting of poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB), and filled with hydrolyzed keratin with loading from 1 to 20 wt % were prepared and their properties were investigated. Mechanical and viscoelastic properties were characterized by tensile test, dynamic mechanical thermal analysis (DMTA) and rheology measurements. The addition of acetyltributyl citrate (ATBC) significantly affected the mechanical properties of the materials. It was found that the filled PLA/PHB/ATBC composite at the highest keratin loading exhibited similar shear moduli compared to the un-plasticized blend as a result of the much stronger interactions between the keratin and polymer matrix compared to composites with lower keratin content. The differences in dynamic moduli for PLA/PHB/ATBC blend filled with keratin depended extensively on the keratin content while loss the factor values progressively decreased with keratin loading. Softening interactions between the keratin and polymer matrix resulted in lower glass transitions temperature and reduced polymer chain mobility. The addition of keratin did not affect the extent of degradation of the PLA/PHB blend during melt blending. Fast hydrolysis at 60 °C was observed for composites with all keratin loadings. The developed keratin-based composites possess properties comparable to commonly used thermoplastics applicable for example as packaging materials.

Sulfobetaines Meet Carboxybetaines: Modulation of Thermo- and Ion-Responsivity, Water Structure, Mechanical Properties, and Cell Adhesion.

A procedure for the preparation of copolymers bearing sulfobetaine and carboxybetaine methacrylic-based monomers by free-radical polymerization is described and discussed. A combination of monomers affects the upper critical solution temperature (UCST) in water and in the presence of a simple NaCl electrolyte while retaining the zwitterionic character. In addition, hydrogel samples were prepared and showed tunable water structure and mechanical properties. The total nonfreezable water content decreases with the amount of carboxybetaine segment in the hydrogel feed and the compression moduli were in a range of 0.7-1.6 MPa. Responses to external conditions such as temperature and ion strength were investigated and a potential application such as modulated thermal detection is proposed. The presence of the carboxylate group in the carboxybetaine segment enables a small fluorescence probe and peptide bearing RDG motif to be attached to polymer and hydrogel samples, respectively. The hydrogel samples functionalized with the RGD motif exhibit controlled cell adhesion. Such synthetic strategy based on combination of different zwitterionic segments offers a simple pathway for the development of zwitterionic materials with programmable properties.

Microbial communities responsible for the degradation of poly(lactic acid)/poly(3-hydroxybutyrate) blend mulches in soil burial respirometric tests.

The microbial communities responsible for the degradation of poly(lactic acid)/poly(3-hydroxybutyrate) (PLA/PHB) blend foils were investigated in 1 year long laboratory soil burial experiments. Different PLA/PHB foils were tested: (a) PLA/PHB original transparent foil, (b) PLA/PHB carbon black filled foil and (c) PLA/PHB black foil previously exposed for 90 days to sun light. The microbiome diversity of these three types of foil was compared with that identified from soil/perlite sample at the beginning of experiment and that developed on a cellulose mat. Culture-dependent and culture-independent (DGGE-cloning) approaches together with PLA, PHB and PLA/PHB degradation plate assays were employed. The cultivation strategy combined with degradation tests permitted the isolation and evaluation of several PLA/PHB blend degrading microorganisms such as members of the genera Bacillus, Paenibacillus, Streptomyces, Rhodococcus, Saccharothrix, Arthrobacter, Aureobasidium, Mortierella, Absidia, Actinomucor, Bjerkandera, Fusarium, Trichoderma and Penicillium. The DGGE-cloning investigation increased the information about the microbial communities occurring during bioplastic degradation detecting several bacterial and fungal taxa and some of them (members of the orders Anaerolineales, Selenomonadales, Thelephorales and of the genera Pseudogymnoascus and Pseudeurotium) were revealed here for the first time. This survey showed the microbiome colonizing PLA/PHB blend foils and permitted the isolation of several microorganisms able to degrade the tested polymeric blends.

Spectral characteristics of carbonyl substituted 2,2'-bithiophenes in polymer matrices and low polar solvents.

The spectral characteristics of monosubstituted derivatives of 2,2'-bithiophene (1-BT) with simple carbonyl substituents, including -COCF3 (trifluoroacetyl, 2-BTCF), -COCH2CN (oxopropanenitrile, 3-BTCN) and -COCH3 (acetyl, 4-BTCE), and the more complex 5'-((9H-fluoren-9-ylidene)methyl)-3-methyl, 5-methyl carboxylate (5-BTFL) were investigated. Absorption and fluorescence spectra and fluorescence lifetimes were measured in solvents with various polarities and compared with those in polymer matrices (polystyrene, PS; polymethyl methacrylate, PMMA; and polyvinyl chloride, PVC). Although the parent, 1-BT, absorbed near 300 nm and exhibited no or weak fluorescence, the substitution of 1-BTwith simple substituents at position 5 resulted in a bathochromic shift of approximately 50 nm or more in absorption and distinct fluorescence above 400 nm. The largest shift in absorption and fluorescence was observed for the complex 5-BTFL with fluorene as a substituent for 1-BT. The most intense fluorescence was observed for the derivative 2-BTCF with trifluoroacetyl as a substituent in the polar PVC matrix. The lifetimes of fluorescence of all substituted 2,2'-bithiophenes were in the range from 0.3 to 3 ns. The polymer matrices increased the intensity of fluorescence to some extent and prolonged the lifetime of the 2,2'-bithiophene derivatives. The reasons for the variation in the fluorescence intensity resulting from the substitution of the parent dimer are discussed.

Structural, optical, and bioimaging characterization of carbon quantum dots solvothermally synthesized from o-phenylenediamine.

Carbon quantum dots as a novel type of carbon nanomaterials have attracted the attention of many researchers because of their unique optical, antibacterial, and anticancer properties as well as their biocompatibility. In this study, for the first time, carbon quantum dots were prepared from o-phenylenediamine dissolved in toluene by a solvothermal route. Subsequently, the prepared carbon quantum dots were encapsulated into polyurethane films by a swelling-encapsulation-shrink method. Analyses of the results obtained by different characterization methods (AFM, TEM, EDS, FTIR, photoluminescence, and EPR) indicate the significant influence of the precursor on structural, chemical, and optical properties. Antibacterial and cytotoxicity tests showed that these dots did not have any antibacterial potential, because of the low extent of reactive oxygen species production, and showed low dark cytotoxicity. By investigating the cellular uptake, it was established that these dots penetrated the HeLa cells and could be used as probes for bioimaging.

Spectral properties of Y-shaped donor-acceptor push-pull imidazole-based fluorophores: comparison between solution and polymer matrices.

The spectral properties of a novel type of Y-shaped fluorophores consisting of an imidazole ring end-capped with two electron-donating N,N-dimethylaminophenyl groups at positions C4 and C5 and one electron-withdrawing cyano group on the imidazole moiety at position C2 were examined. The π-linker separating the 4,5-bis[4-(N,N-dimethylamino)phenyl]-1H-imidazole donor moiety and the cyano group comprises 1,4-phenylene (1), (E)-phenylethenyl (2), (E)-phenylbuta-1,3-dienyl (3), biphenyl (4), (E)-phenylethenylphenyl (5) and phenylethynylphenyl (6) conjugated paths. The absorption and fluorescence spectra were obtained in toluene, dichloromethane, acetonitrile and methanol and in polymer matrices such as polystyrene (PS), poly(methyl methacrylate) (PMMA) and poly(vinylchloride) (PVC). The most intense absorption bands of fluorophores 1-6 were observed within the range of 283 to 330 nm. Less intense but longer-wavelength absorption bands designated as charge-transfer bands were observed at approximately 380-430 nm depending on the medium. The fluorophores exhibited strong fluorescence in the visible region with a Stokes shift of approximately 4300-5800 cm(-1) in non-polar toluene and polystyrene, whereas very low intensity of fluorescence was observed with a Stokes shift in the 6500-7800 cm(-1) region in polar methanol and acetonitrile. The large Stokes shift indicates a large difference in the spatial arrangement of the chromophore in the absorbing and emitting states. A relatively intense fluorescence (quantum yields of 0.12-0.69) was observed only for derivative 1 in all media except methanol. The fluorophores doped in matrices yielded more intense fluorescence compared with the fluorescence in liquid media. The use of solid polymer matrices lowers the probability of forming non-emissive excited states. The fluorescence lifetimes were short (1-4 ns) for all of the fluorophores in solvents and in polymer matrices.

Preparation and spectral characterization of fluorescence probes based on 4-N,N-dimethylamino benzoic acid and sterically hindered amines.

The adducts of simple chromophore 4-N,N-dimethylamino benzoic acid with 2,2,6,6-tetrametyl-4-hydroxy- or 4-amino-piperidine were examined as fluorescence probes (spin double sensors) to monitor radical processes. The links in the adducts were either an ester or amide group, and the sterically hindered amines were in the form of -NH, -NO• and -NOR. The spectral properties of the three related derivatives (esters or amides) were quite similar. The maxima of the absorption spectra were in the range of 295-315 nm, and the maximum of fluorescence was located in the range of 330-360 nm, depending on the polarity of the solvent. In polar solvents, a red-shifted fluorescence band at 460-475 nm was observed. The fluorescence of these derivatives was rather weak as compared to anthracene under the same conditions. The Stokes shift was large, as high as 6,000 cm(-1), indicating the formation of a twisted intra-molecular charge transfer (TICT) state. No large differences in Stokes shifts were observed in polymer matrices of poly(methyl methacrylate), polystyrene and poly(vinyl chloride). The extent of intramolecular quenching was expressed as Φ(NX)/Φ(NO) (X = H, NOR) and was in the range of 1-3 in solution and as high as 8 in polymer matrices. The low efficiency of intramolecular quenching limits the application of these new adducts as fluorescence probes for the monitoring of radical processes in solution but favors their application in polymer matrices.

Spectral properties of substituted coumarins in solution and polymer matrices.

The absorption and fluorescence spectra of substituted coumarins (2-oxo-2H-chromenes) were investigated in solvents and in polymer matrices. The substitutions involved were: (1) by groups with varying electron donating ability such as CH3, OCH3 and N(CH3)2, mainly, but not exclusively, in positions 7 and (2), by either CHO or 4-PhNHCONHN=CH- in position 3. While the spectra of non-substituted coumarin-3-carbaldehyde has absorptions at approximately 305 and 350 nm, substitution at position 7 leads to remarkable changes in the shape of the absorption spectrum and shifts the absorption to a longer wavelength. Similarly, the replacement of the formyl group with a semicarbazide group substantially influences the shape of the absorption spectrum, and coumarins which have only N(CH3)2 in position 7 experience small changes. These changes are associated with the increasing intramolecular charge transfer (ICT) character and increasing conjugation length of the chromophoric system, respectively, in the studied molecules. The fluorescence is almost negligible for derivatives which have H in this position. With increasing electron donating ability, and the possibility of a positive mesomeric (+M) effect of the substituent in position 7 of the coumarin moiety, the fluorescence increases, and this increase is most intense when N(CH3)2 substitutes in this position, for both 3-substituted derivatives. Spectral measurements of the studied coumarins in polymer matrices revealed that the absorption and fluorescence maxima lay within the maxima for solvents, and that coumarins yield more intense fluorescence in polymer matrices than when they are in solution. The quantum yield of derivatives which have a dimethylamino group in position 7 in polymer matrices approaches 1, and the fluorescence lifetime is within the range of 0.5-4 ns. The high quantum yield of 7-dimethylamino derivatives qualifies them as laser dyes which have k(F) higher than k(nr) in the given medium. This is caused by stiffening of the coumarin structure in polar polymer matrices, such as PMMA and PVC, due to higher micro-viscosity than in solution and intermolecular dipole-dipole interaction between chromophore (dopant) and matrix.

Push-pull fluorophores based on imidazole-4,5-dicarbonitrile: a comparison of spectral properties in solution and polymer matrices.

Spectral properties of novel type of fluorophores consist of a π-conjugated system end-capped with an electron-donating N,N-dimethylaminophenyl group and an electron-withdrawing imidazole-4,5-dicarbonitrile moiety were examined. An additional π-linker separating these two structural units comprises simple bond (B1P), phenyl (B2B), styryl (B3S) and ethynylphenyl (B4A) moieties. The absorption and fluorescence spectra were taken in cyclohexane, chloroform, acetonitrile, methanol and in polymer matrices such as polystyrene, poly(methyl methacrylate) and poly(vinylchloride). The longest-wavelength absorption band was observed in the range of 300 to 400 nm. Intense fluorescence with quantum yields of 0.2 to 1.0 was observed in cyclohexane, chloroform and in polymer matrices within the range of 380 to 500 nm. The fluorescence was strongly quenched in neat acetonitrile and methanol. The fluorescence lifetimes are in the range of 1-4 ns for all measured fluorophores. The large Stokes shift (4,000 to 8,000 cm(-1)) indicates a large difference in the spatial arrangement of the chromophore in the absorbing and the emitting states. The observed fluorescence of all fluorophores in chloroform was quenched by 1-oxo-2,2,6,6-tetramethyl-4-hydroxy piperidine by the diffusion-controlled bimolecular rate (cca 2 × 10(10) L mol(-1) s(-1)). Polar solvents such as acetonitrile and methanol quenched the fluorescence as well but probably via a different mechanism.

Exchange Counterion in Polycationic Hydrogels: Tunability of Hydrophobicity, Water State, and Floating Capability for a Floating pH Device.

Smart gel materials are capable of controlling and switching swelling, water state, and wettability properties triggered by external stimuli. In this study, we fabricated a series of polyelectrolyte hydrogels bearing a 3-trimethylammoniumpropyl pendant to a methacrylamide-based backbone and examined the switchability with hydrophobic-like counteranions. The exchange between the initial chloride and camphor sulfate (CaS), dodecyl sulfate (DS), and perfluorooctanoate (PFO) counterions was investigated. The kinetics of the exchange showed that the fast exchange (within 4 h) of PFO allowed for a favorable coordination for ion pairing, resulting in a decrease in hydration. The reversibility of the exchange to the Cl- ion was only enabled for the CaS ion due to its bulkiness, while the PFO and DS hydrogels were unable to exchange, even by using tetrabutylammonium chloride, which is a structurally similar reagent, due to aggregation or the coagulates in the collapsed state of the linear tails of the counterions. The hydrogels exhibited a modulable water state and water swelling. Moreover, the hydrogels containing DS and PFO, as counterions, showed surface hydrophobic (contact angle 90°) and high hydrophobic (110°) behavior, respectively. The Raman spectrometry fluorescence with a pyrene probe indicated an increase in strong hydrogen-bonded water molecules, water confinement, and hydrophobic domains in the PFO hydrogel. Moreover, the PFO-modified hydrogel demonstrated a free-floating ability on the water surface, with a strong water repellency, showing that it has the potential to be applied in a floating pH detection device to distinguish between volatile and nonvolatile bases in a controlled manner.

Multifunctional Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Porous Materials for CO2 Uptake and Iodine Adsorption.

In this study, two different types of hybrid porous organic polymers (POPs), polyhedral oligomeric silsesquioxane tetraphenylpyrazine (POSS-TPP) and tetraphenylethene (POSS-TPE), were successfully synthesized through the Friedel-Crafts polymerization of tetraphenylpyrazine (TPP) and tetraphenylethene (TPE), respectively, with octavinylsilsesquioxane (OVS) as node building blocks, in the presence of anhydrous FeCl3 as a catalyst and 1,2-dichloroethane at 60 °C. Based on N2 adsorption and thermogravimetric analyses, the resulting hybrid porous materials displayed high surface areas (270 m2/g for POSS-TPP and 741 m2/g for POSS-TPE) and outstanding thermal stabilities. Furthermore, as-prepared POSS-TPP exhibited a high carbon dioxide capacity (1.63 mmol/g at 298 K and 2.88 mmol/g at 273 K) with an excellent high adsorption capacity for iodine, reaching up to 363 mg/g, compared with the POSS-TPE (309 mg/g).

Properties and Degradation Performances of Biodegradable Poly(lactic acid)/Poly(3-hydroxybutyrate) Blends and Keratin Composites.

From environmental aspects, the recovery of keratin waste is one of the important needs and therefore also one of the current topics of many research groups. Here, the keratin hydrolysate after basic hydrolysis was used as a filler in plasticized polylactic acid/poly(3-hydroxybutyrate) blend under loading in the range of 1-20 wt%. The composites were characterized by infrared spectroscopy, and the effect of keratin on changes in molar masses of matrices during processing was investigated using gel permeation chromatography (GPC). Thermal properties of the composites were investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of keratin loading on the mechanical properties of composite was investigated by tensile test and dynamic mechanical thermal analysis. Hydrolytic degradation of matrices and composites was investigated by the determination of extractable product amounts, GPC, DSC and NMR. Finally, microbial growth and degradation were investigated. It was found that incorporation of keratin in plasticized PLA/PHB blend provides material with good thermal and mechanical properties and improved degradation under common environmental conditions, indicating its possible application in agriculture and/or packaging.

Bioleaching of Manganese Oxides at Different Oxidation States by Filamentous Fungus Aspergillus niger.

This work aimed to examine the bioleaching of manganese oxides at various oxidation states (MnO, MnO·Mn2O3, Mn2O3 and MnO2) by a strain of the filamentous fungus Aspergillus niger, a frequent soil representative. Our results showed that the fungus effectively disintegrated the crystal structure of selected mineral manganese phases. Thereby, during a 31-day static incubation of oxides in the presence of fungus, manganese was bioextracted into the culture medium and, in some cases, transformed into a new biogenic mineral. The latter resulted from the precipitation of extracted manganese with biogenic oxalate. The Mn(II,III)-oxide was the most susceptible to fungal biodeterioration, and up to 26% of the manganese content in oxide was extracted by the fungus into the medium. The detected variabilities in biogenic oxalate and gluconate accumulation in the medium are also discussed regarding the fungal sensitivity to manganese. These suggest an alternative pathway of manganese oxides' biodeterioration via a reductive dissolution. There, the oxalate metabolites are consumed as the reductive agents. Our results highlight the significance of fungal activity in manganese mobilization and transformation. The soil fungi should be considered an important geoactive agent that affects the stability of natural geochemical barriers.

Fungal Mobilization of Selenium in the Presence of Hausmannite and Ferric Oxyhydroxides.

Bioleaching of mineral phases plays a crucial role in the mobility and availability of various elements, including selenium. Therefore, the leachability of selenium associated with the surfaces of ferric and manganese oxides and oxyhydroxides, the prevailing components of natural geochemical barriers, has been studied in the presence of filamentous fungus. Both geoactive phases were exposed to selenate and subsequently to growing fungus Aspergillus niger for three weeks. This common soil fungus has shown exceptional ability to alter the distribution and mobility of selenium in the presence of both solid phases. The fungus initiated the extensive bioextraction of selenium from the surfaces of amorphous ferric oxyhydroxides, while the hausmannite (Mn3O4) was highly susceptible to biodeterioration in the presence of selenium. This resulted in specific outcomes regarding the selenium, iron, and manganese uptake by fungus and residual selenium concentrations in mineral phases as well. The adverse effects of bioleaching on fungal growth are also discussed.

Photoactive and antioxidant nanochitosan dots/biocellulose hydrogels for wound healing treatment.

Bacterial infection and their resistance to known antibiotics delays wound healing. In this study, nanochitosan dots (nChiD) produced by gamma irradiation have been encapsulated in bacterial cellulose (BC) polymer matrix to study the antibacterial potentials of these nanocomposites and their possible usage in wound healing treatment (scratch assay). Detailed analyses show that nChiDs have disc-like shape and average diameter in the range of 40 to 60 nm depending of the applied dose. All nChiDs as well as BC-nChiD nanocomposites emit green photoluminescence independently on the excitation wavelengths. The new designed nanocomposites do not have a cytotoxic effect; antioxidant analysis shows their moderate radical scavenging activity whereas antibacterial properties show significant growth inhibition of strains mostly found in difficult-to-heal wounds. The obtained results confirm that new designed BC-nChiD nanocomposites might be potential agent in wound healing treatment.

Correction: Gamma ray assisted modification of carbon quantum dot/polyurethane nanocomposites: structural, mechanical and photocatalytic study.

[This corrects the article DOI: 10.1039/C9RA00500E.].

Functional Polymers and Polymeric Materials From Renewable Alpha-Unsaturated Gamma-Butyrolactones.

Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered γ-butyrolactone ring represent suitable candidates to replace sources of fossil origin. α-Methylene-γ-butyrolactone, ß-hydroxy-α-methylene-γ-butyrolactone, and ß- and γ-methyl-α-methylene-γ-butyrolactones bearing exocyclic double bond are available directly by isolation from plants or derived from itaconic or levulinic acids available from biomass feedstock. Exocyclic double bond with structural similarity with methacrylates is highly reactive in chain-growth polymerization. Reaction involves the linking of monomer molecules through vinyl double bonds in the presence of initiators typical for radical, anionic, zwitterionic, group-transfer, organocatalytic, and coordination polymerizations. The formed polymers containing pendant ring are characterized by high glass transition temperature (T g > 195°C) and render decent heat, weathering, scratch, and solvent resistance. The monomers can also be hydrolyzed to open the lactone ring and form water-soluble monomers. Subsequent radical copolymerization in the presence of cross-linker can yield to hydrogels with superior degree of swelling and highly tunable characteristics, depending on the external stimuli. The five-membered lactone ring allows copolymerization of these compounds by ring opening polymerization to provide polyesters with preserved methylene functionality. In addition, both the lactone ring and the methylene double bond can be attacked by amines. Polyaddition with di- or multi-amines leads to functional poly(amidoamines) with properties tunable by structure of the amines. In this mini-review, we summarize the synthetic procedures for preparation of polymeric materials with interesting properties, including thermoplastic elastomers, acrylic latexes, stimuli-sensitive superabsorbent hydrogels, functional biocompatible polyesters, and poly(amidoamines).