Carbohydrate-Based Reprocessable and Healable Covalent Adaptable Biofoams.

Polymeric foams derived from bio-based resources and capable of self-healing and recycling ability are of great demand to fulfill various applications and address environmental concerns related to accumulation of plastic wastes. In this article, a set of polyester-based covalent adaptable biofoams (CABs) synthesized from carbohydrates and other bio-derived precursors under catalyst free conditions to offer a sustainable alternative to conventional toxic isocyanate-based polyurethane foams is reported. The dynamic ß-keto carboxylate linkages present in these biofoams impart self-healing ability and recyclability to these samples. These CABs display adequate tensile properties especially compressive strength (≤123 MPa) and hysteresis behavior. The CABs swiftly stress relax at 150 °C and are reprocessable under similar temperature conditions. These biofoams have displayed potential for use as attachment on solar photovoltaics to augment the output efficiency. These CABs with limited swellability in polar protic solvents and adequate mechanical resilience are suitable for other commodity applications.

Closed-loop recyclable and biodegradable thioester-based covalent adaptable networks.

Closed-loop recyclable and biodegradable aliphatic covalent adaptable networks (CANs) based on dynamic ß-CO thioester linkages that exhibit a service temperature beyond 100 °C are reported. These CANs possessing tensile strength and modulus values of up to 0.3 and 3 MPa, respectively, effectively undergo stress relaxation above 100 °C. The samples exhibit creep resistance ability and low hysteresis loss, and are repeatedly reprocessable at 120 °C. These CANs are depolymerizable to monomers under mild conditions and lose notable mechanical strength (92.4%) and weight (76.5%) within ∼35 days under natural biodegradation conditions.

Stress-Induced Shape-Shifting Materials Possessing Autonomous Self-Healing and Scratch-Resistant Ability.

Covalent adaptable networks (CANs) capable of both shape-shifting and self-healing ability offer a viable alternative to 4D printing technology to gain access to various complex shapes in a simplified manner. However, most of the reported CANs exhibit shape-shifting ability in the presence of temperature, light or chemical stimuli, which restricts their further utilization as realization of such a controlled environment is not feasible under complex scenarios. Herewith, we report a set of CANs based on a room-temperature exchangeable thia-Michael adduct, which undergoes rearrangement in network topology on application of external stress. These CANs with tensile strength (≤6 MPa) and modulus (≤71.4 MPa) adopt to any programmed shape under application of nominal stress. The CANs also exhibit stress-induced recyclability, self-welding and self-healing ability under ambient conditions. The transparency and ambient condition self-healing ability render these CANs to be utilized as scratch-resistant coatings on display items.

Healable, Recyclable, and Programmable Shape Memory Organogels Based on Highly Malleable Catalyst-Free Carboxylate Linkages.

The development of healable and recyclable organogels possessing responsive abilities is mainly hindered by the unavailability of many dynamic covalent linkages that undergo exchange reaction below the boiling temperature of organic swelling medium. Furthermore, the exchange is desired to be effective under catalyst-free conditions to circumvent the issue of catalyst leaching during the swelling process. Especially, imparting swift reversibility to thermostable carboxylate linkages is challenging. In this approach, we have utilized the ß-keto anchimeric assistance as the tool to induce swift reversibility into the conventional carboxylate linkage under mild temperature (∼70-90 °C) and catalyst-free conditions. Using this ß-keto carboxylate linkage as an associative bond exchange mean, strong (tensile strength = 0.3 MPa) and stretchable (ultimate elongation ≈ 600%) covalent adaptable organogels (CAOs) with anisotropic swelling, remoldable, self-healing, and shape memory ability are derived from commercially available precursors. The shape memory ability of these samples shows dependency on the shape fixing time and can be programmed, targeting further applications. Soft actuators may be fabricated from the CAOs using temperature and solvent as the activating tools. This research demonstrates that the conventional carboxylate linkages can be made labile under mild conditions for further applications.

Effect of NaCl concentration on stability of a polymer-Ag nanocomposite based Pickering emulsion: validation via rheological analysis with varying temperature.

The utility of a Pickering emulsion (PEm) under saline conditions is strongly dependent on the stability of the emulsion in the presence of different salt concentrations. In this study, we have evaluated the effect of NaCl and temperature on the stability of a polyacryloyl hydrazide (PAHz)-Ag nanocomposite (NC) based PEm utilizing ocular observation, an optical microscope with a thermal stage, TGA, DLS, electrical conductivity, and rheological studies at different temperatures. The creaming stability of PEm in the presence of salt concentrations in the range of 0.5 to 5.0 wt% was evaluated by adding different amounts of PAHz-Ag NC stabilizer. The effect of NaCl on emulsion stability is strongly dependent on the aggregation behaviour of the nanocomposites, showing signs of aggregation at low NaCl concentration (<3 wt%) and re-dispersion at high NaCl concentration (>3 wt%). As per the microscopy analysis, 25 wt% of PAHz-Ag NC was sufficient to stabilize the PEm for a period of up to 7 days in the presence of salt concentrations up to 3 wt% in the aqueous layer at 95 °C. Thus, the balance of ionic strength provides an important insight into the nature of nanocomposite interactions in emulsion systems and a possible mechanism for designing emulsion properties via salt inclusion.

Stable & re-dispersible polyacryloyl hydrazide-Ag nanocomposite Pickering emulsions.

Freeze drying and re-dispersibility of oil-in-water (o/w) emulsions is important from the perspective of storage, transportation and usability. A set of stable and re-dispersible o/w emulsions using polyacryloyl hydrazide (PAHz) capped Ag nanoparticles (NP) as the stabilizer is reported in which the NP size (Davg) and PAHz concentration collectively controlled the stability and re-dispersibility of the emulsion system. O/w emulsions prepared using different concentrations of PAHz (0.05-0.25 g mL-1) and sizes of Ag NPs (10-25 nm) were analyzed by DLS, IFT, contact angle, SEM, and rheological studies. The emulsion stabilized by 0.05 g mL-1 of PAHz and Ag NPs (Davg ≈ 20 nm, 5 wt% PAHz-Ag NPs) was unstable against coalescence, exhibited maximum oil leakage during freeze-drying and lacked re-dispersibility. The stability of the Pickering emulsions was inversely proportional to the Davg of the Ag NPs. The presence of Ag NPs possessing Davg ≈ 10 nm and 0.25 g mL-1 of PAHz in the aqueous phase (25 wt% PAHz-Ag NPs) stabilized the Pickering emulsions for up to 30 days without any sign of creaming and the oil powders (oil content ≈ 98%) obtained after freeze drying exhibited adequate re-dispersibility in aqueous media. In addition, the emulsion stabilized by 25 wt% PAHz-Ag NPs showed maximum recovery of the viscosity value after re-dispersion and exhibited similar shear-thinning behavior to that of the original sample. Furthermore, the trends of moduli vs. frequency for the re-dispersed samples were similar to that of the original samples suggesting that the structural arrangements between Ag NPs and oil droplets were least affected by the drying process. Thus, we conclude that o/w emulsions stabilized by PAHz-Ag NPs can be a potential alternative to produce stable oil powders or gels for industrial applications.

Dye-Labeled Polyacryloyl Hydrazide-Ag Nanoparticle Fluorescent Probe for Ultrasensitive and Selective Detection of Au Ion.

The efficiency of a fluorescence sensing device based on metal-enhanced fluorescence (MEF) is dependent on the optimization of interaction between the fluorophore and the metal nanoparticle (NP). Herewith, ultrasensitive and selective turn-on sensing of Au3+ is achieved by using a suitable combination of fluorophore and metal NP system through sequential MEF effect. Dansyl hydrazide-tagged Ag NPs in the polyacryloyl hydrazide cavity are utilized to sense the picomolar concentration of Au3+ in aqueous media. We demonstrated that the selective Au3+ sensing is due to the selective deposition of Au on the Ag NP surface over the 16 other metal ions studied. The sensitivity is assigned to the strong overlapping of the emission band of the fluorophore with the surface plasmon band of the Au and improvement of fluorescence signal through successive MEF by Ag and Au colloids. The sensing is associated with a fivefold increase in fluorescence intensity and appearance of violet color of the solution. These luminescent Ag-Au bimetallic NPs may be utilized to trace cancer cells in biological systems and for cell imaging applications.

General Reagent Free Route to pH Responsive Polyacryloyl Hydrazide Capped Metal Nanogels for Synergistic Anticancer Therapeutics.

Herewith, we report a facile synthesis of pH responsive polyacryloyl hydrazide (PAH) capped silver (Ag) or gold (Au) nanogels for anticancer therapeutic applications. A cost-effective instant synthesis of PAH-Ag or PAH-Au nanoparticles (NPs) possessing controllable particle diameter and narrow size distribution was accomplished by adding AgNO3 or AuCl to the aqueous solution of PAH under ambient conditions without using any additional reagent. PAH possessing carbonyl hydrazide pendant functionality served as both reducing and capping agent to produce and stabilize the NPs. The stability analysis by UV-vis, dynamic light scattering, and transmission electron microscopy techniques suggested that these NPs may be stored in a refrigerator for at least up to 2 weeks with negligible change in conformation. The average hydrodynamic size of PAH-Ag NPs synthesized using 0.2 mmol/L AgNO3 changed from 122 to 226 nm on changing the pH of the medium from 5.4 to 7.4, which is a characteristic property of pH responsive nanogel. Camptothecin (CPT) with adequate loading efficiency (6.3%) was encapsulated in the PAH-Ag nanogels. Under pH 5.4 conditions, these nanogels released 78% of the originally loaded CPT over a period of 70 h. The antiproliferative potential of PAH-Ag-CPT nanogels (at [CPT]=0.6 µg/mL) against MCF-7 breast adeno-carcinoma cells were ∼350% higher compared to that of the free CPT as evidenced by high cellular internalization of these nanogels. Induction of apoptosis in MCF-7 breast adeno-carcinoma cells by PAH-Ag-CPT nanogels was evidenced by accumulation of late apoptotic cell population. Drug along with the PAH-Ag NPs were also encapsulated in a pH responsive hydrogel through in situ gelation at room temperature using acrylic acid as the cross-linker. The resulting hydrogel released quantitative amounts of both drug and PAH-Ag NPs over a period of 16 h. The simplicity of synthesis and ease of drug loading with efficient release render these NPs a viable candidate for various biomedical applications, and moreover this synthetic procedure may be extended to other metal NPs.

Polyacryloyl hydrazide: an efficient, simple, and cost effective precursor to a range of functional materials through hydrazide based click reactions.

Preparation and studies of ion exchangeable epoxy resins, stimuli responsive hydrogels, and polymer-dye conjugates have been accomplished through hydrazide based click reactions using polyacryloyl hydrazide (PAH) as the precursor. A convenient synthesis of PAH with quantitative functionality was achieved by treatment of polymethyl acrylate with hydrazine hydrate in the presence of tetra-n-butyl ammonium bromide. PAH was cured with bisphenol A diglycidyl ether (BADGE) at 60 °C to form transparent resins with superior mechanical properties (tensile strength = 2-40 MPa, Young's modulus = 3.3-1043 MPa, and ultimate elongation = 9-75%) compared to the conventional resins prepared using triethylene tetramine. The resins exhibited higher ion exchange capacities (1.2-6.3 mmol/g) compared to the commercial AHA ammonium-type (Tokuyama Co., Japan) membranes. An azo dye with aldehyde functionality was covalently attached to PAH through hydrazone linkage, and the dye labeled PAH exhibited colorimetric sensing ability for base and acids up to micromolar concentration. The swelling of the PAH based hydrogel varied in the range 4-450% depending on the pH and temperature of the medium. The hydrogels gradually released 30% of the original encapsulated dye in a period of 200 h. PAH-hydroxy naphthaldehyde conjugate released 75% of the original loading in ∼11 days at 37 °C and pH 5.0 through cleavage of the -CONHN═C- linkage. The study depicts the versatility of PAH as a precursor and inspires synthesis of a range of new materials based on PAH in the future.

Polyacryloyl hydrazide based injectable & stimuli responsive hydrogels with tunable properties.

The synthesis and characterization of a series of injectable and stimuli responsive hydrogels based on polyacryloyl hydrazide have been accomplished using dimethyl 2,2'-thiodiacetate, acrylic acid (AA), diethyl malonate and polyethylene glycol diacrylate (PEGDA) as cross-linkers through a chemical or dual cross-linking pathway. The cross-linking reactions were carried out at room temperature or 70 °C to synthesize uniform and transparent gels. The swelling ratios ≈ 10-800% of the hydrogels depended on the type and concentration of the cross-linker, temperature and pH of the medium. A suitable combination of chemical and physical cross-linking was necessary to achieve optimum storage modulus of the gels. The yield stress of the gels synthesized using cross-linker concentrations up to 0.7 mol L-1 was observed above 10% strain and the viscosity decreased by at least two orders of magnitude upon increasing the shear rate by 1000 times suggesting that the gels may be smoothly injected through the needle. The gels released up to 10-84% of the total encapsulated Rhodamine B in a controlled manner over a period of 120 h under physiological conditions. The gels prepared using cross-linker concentrations up to 1.3 mol L-1 exhibited excellent water retention capacity (>95%) up to 40 days. Samples synthesized using AA and PEGDA as cross-linkers exhibited excellent cytocompatibility and are potential candidates for controlled delivery as well as non-evasive biomedical applications.

Surface characterization and protein interactions of segmented polyisobutylene-based thermoplastic polyurethanes.

The surface properties and biocompatibility of a class of thermoplastic polyurethanes (TPUs) with applications in blood-contacting medical devices have been studied. Thin films of commercial TPUs and novel polyisobutylene (PIB)-poly(tetramethylene oxide) (PTMO) TPUs were characterized by contact angle measurements, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM) imaging. PIB-PTMO TPU surfaces have significantly higher C/N ratios and lower amounts of oxygen than the theoretical bulk composition, which is attributed to surface enrichment of PIB. Greater differences in the C/N ratios were observed with the softer compositions due to their higher relative amounts of PIB. The contact angles were higher on PIB-PTMO TPUs than on commercial polyether TPUs, indicating lower surface energy. AFM imaging showed phase separation and increasing domain sizes with increasing hard segment content. The biocompatibility was investigated by quantifying the adsorption of fouling and passivating proteins, fibrinogen (Fg) and human serum albumin (HSA) respectively, onto thin TPU films spin coated onto the electrode of a quartz crystal microbalance with dissipation monitoring (QCM-D). Competitive adsorption experiments were performed with a mixture of Fg and albumin in physiological ratio followed by binding of GPIIb-IIIa, the platelet receptor ligand that selectively binds to Fg. The QCM-D results indicate similar adsorbed amounts of both Fg and HSA on PIB-PTMO TPUs and commercial TPUs. The strength of the protein interactions with the various TPU surfaces measured with AFM (colloidal probe) was similar among the various TPUs. These results suggest excellent biocompatibility of these novel PIB-PTMO TPUs, similar to that of polyether TPUs.

Long term in vitro biostability of segmented polyisobutylene-based thermoplastic polyurethanes.

Long term in vitro biostability of thermoplastic polyurethanes (TPUs) containing mixed polyisobutylene (PIB)/poly(tetramethylene oxide) (PTMO) soft segment was studied under accelerated conditions in 20% H(2)O(2) solution containing 0.1M CoCl(2) at 50 °C to predict resistance to metal ion oxidative degradation (MIO) in vivo. The PIB-based TPUs showed significant oxidative stability as compared to the commercial controls Pellethane 2363-55D and 2363-80A. After 12 weeks in vitro the PIB-PTMO TPUs with 10-20% PTMO in the soft segment showed 6-10% weight loss whereas the Pellethane TPUs degraded completely in about 9 weeks. Attenuated total reflectance Fourier transform infrared spectroscopy confirmed the degradation of Pellethane samples via MIO by the loss of the ∼1110 cm(-1) aliphatic C-O-C stretching peak height attributed to chain scission, and the appearance of a new peak at ∼1174 cm(-1) attributed to crosslinking. No such changes were apparent in the spectra of the PIB-based TPUs. The PIB-based TPUs exhibited 10-30% drop in tensile strength compared to 100% for the Pellethane TPUs after 12 weeks. The molecular weight of the PIB-based TPUs decreased slightly (10-15%) at 12 weeks. The Pellethane TPUs showed a dramatic decrease in M(n) and an increase in low molecular weight degradation product. Scanning electron microscopy (SEM) showed severe cracking in the Pellethane samples after 2 weeks, whereas the PIB-based TPUs exhibited a continuous surface morphology. The weight loss, tensile, and SEM data correlate well with each other and indicate excellent biostability of these materials.

Peptide surface modification of P(HEMA-co-MMA)-b-PIB-b-P(HEMA-co-MMA) block copolymers.

Peptide surface modification of poly[(methyl methacrylate-co-hydroxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-hydroxyethyl methacrylate)] P(MMA-co-HEMA)-b-PIB-b-P(MMA-co-HEMA) triblock copolymers with different HEMA/MMA ratios has been accomplished using an efficient synthetic procedure. The triblock copolymers were reacted with 4-fluorobenzenesulfonyl chloride (fosyl chloride) in pyridine to obtain the activated polymers [poly{(methyl methacrylate-co-fosyloxyethyl methacrylate)-b-isobutylene-b-(methyl methacrylate-co-fosyloxyethyl methacrylate)}] P(MMA-co-FEMA)-b-PIB-b-P(MMA-co-FEMA), with an activating efficiency of 80-90%. The resulting polymers were soluble in chloroform, and their solutions were used to coat thin uniform films with a predetermined thickness on smooth steel surfaces. The presence of reactive activating groups on the film surface was confirmed by X-ray photoelectron spectroscopy (XPS), dye labeling, and confocal laser scanning microscopic studies. Activation of the triblock copolymer films was also achieved under heterogeneous conditions in polar (acetonitrile) and nonpolar (hexanes) media. The extent of activation was controlled by varying the dipping time and polarity of the medium. Peptide attachment was accomplished by immersing the coated steel strips into aqueous buffer solution of Gly-Gly or GYIGSR. XPS and solubility studies revealed successful attachment of peptides to the polymer surface. Virtually all remaining activating groups were successfully replaced in the subsequent step by a treatment with Tris(hydroxymethyl)amino methane in a buffered methanol/water mixture.