Effects of Commonly used Surfactants, Poloxamer 188 and Tween 80, on the Drug Transport Capacity of Intestinal Glucose Transporters.

Some glycoside drugs can be transported through intestinal glucose transporters (IGTs). The surfactants used in oral drug preparations can affect the function of transporter proteins. This study aimed to investigate the effect of commonly used surfactants, Poloxamer 188 and Tween 80, on the drug transport capacity of IGTs. Previous studies have shown that gastrodin is the optimal drug substrate for IGTs. Gastrodin was used as a probe drug to evaluate the effect of these two surfactants on intestinal absorption in SD rats through pharmacokinetic and in situ single-pass intestinal perfusion. Then, the effects of the two surfactants on the expression of glucose transporters and tight-junction proteins were examined using RT-PCR and western blotting. Additionally, the effect of surfactants on intestinal permeability was evaluated through hematoxylin-eosin staining. The results found that all experimental for Poloxamer 188 (0.5%, 2.0% and 8.0%) and Tween 80 (0.1% and 2.0%) were not significantly different from those of the blank group. However, the AUC(0-∞) of gastrodin increased by approximately 32% when 0.5% Tween 80 was used. The changes in IGT expression correlated with the intestinal absorption of gastrodin. A significant increase in the expression of IGTs was observed at 0.5% Tween 80. In conclusion, Poloxamer 188 had minimal effect on the drug transport capacity of IGTs within the recommended limits of use. However, the expression of IGTs increased in response to 0.5% Tween 80, which significantly enhanced the drug transport capacity of IGTs. However, 0.1% and 2.0% Tween 80 had no significant effect.

A Multifunctional Contrast Agent for 19F-Based Magnetic Resonance Imaging.

Magnetic resonance imaging, MRI, relying on 19F nuclei has attracted much attention, because the isotopes exhibit a high gyromagnetic ratio (comparable to that of protons) and have 100% natural abundance. Furthermore, due to the very low traces of intrinsic fluorine in biological tissues, fluorine labeling allows easy visualization in vivo using 19F-based MRI. However, one of the drawbacks of the available fluorine tracers is their very limited solubility in water. Here, we detail the design and preparation of a set of water-compatible fluorine-rich polymers as contrast agents that can enhance the effectiveness of 19F-based MRI. The agents are synthesized using the nucleophilic addition reaction between poly(isobutylene-alt-maleic anhydride) copolymer and a mixture of amine-appended fluorine groups and polyethylene glycol (PEG) blocks. This allows control over the polymer architecture and stoichiometry, resulting in good affinity to water solutions. We further investigate the effects of introducing additional segmental mobility to the fluorine moieties in the polymer, by inserting a PEG linker between the moieties and the polymer backbone. We find that controlling the polymer stoichiometry and introducing additional segmental mobility enhance the NMR signals and narrow the peak profile. In particular, we assess the impact of the PEG linker on T2* and T1 relaxation times, using a series of gradient-recalled echo images with varying echo times, TE, or recovery time, TR, respectively. We find that for equivalent concentrations, the PEG linker greatly increases T2*, while maintaining high T1 values, as compared to polymers without this linker. Phantom images collected from these compounds show bright signals over a background with high intensities.

Engineering the Bio-Nano Interface Using a Multifunctional Coordinating Polymer Coating.

In the past three decades, interest in using nanoparticles as diagnostic tools to interrogate various biosystems has witnessed remarkable growth. For instance, it has been shown that nanoparticle probes enable the study of cellular processes at the single molecule level. These advances provide new opportunities for understanding fundamental problems in biology, innovation in medicine, and the treatment of diseases. A multitude of nanoparticles have been designed to facilitate in vitro or in vivo sensing, imaging, and diagnostics. Some of those nanoparticle platforms are currently in clinical trials or have been approved by the U.S. Food and Drug Administration. Nonetheless, using nanoparticles in biology is still facing several obstacles, such as poor colloidal stability under physiological conditions, nonspecific interactions with serum proteins, and low targeting efficiency in biological fluids, in addition to issues of uncontrolled biodistribution and cytotoxicity. All these problems are primarily controlled by the surface stabilizing coating used.In this Account, we summarize recent progress made in our laboratory focused on the development of multifunctional polymers as coordinating ligands, to tailor the surface properties of nanoparticles and facilitate their application in biology. We first detail the advantageous features of the coating strategy, followed by a discussion of the key parameters in the ligand design. We then describe the synthesis and use of a series of multicoordinating polymers as ligands optimized for coating quantum dots (QDs), gold nanoparticles (AuNPs), and magnetic nanoparticles (MNPs), with a focus on (i) how to improve the colloidal stability and antifouling performance of materials in biological conditions; (ii) how to design highly compact coating, without compromising colloidal stability; and (iii) how to tailor the surface functionalities to achieve conjugation to target biomolecules. We also highlight the ability of a phase transfer strategy, mediated by UV irradiation, to promote rapid ligand exchange while preserving the integrity of key functional groups. We then summarize the bioconjugation approaches applied to polymer-coated nanoparticles, with emphasis on the ability of metal-histidine self-assembly and click chemistry, to control the final nanoparticle bioconjugates. Finally, we demonstrate the use of polymer-coated nanoparticles for sensor design based on redox-active interactions and peptide-mediated intracellular delivery. We anticipate that the coating design presented in this Account would advance the integration of nanoparticles into biology and medicine.

Compact, "Clickable" Quantum Dots Photoligated with Multifunctional Zwitterionic Polymers for Immunofluorescence and In Vivo Imaging.

We detail the preparation of highly fluorescent quantum dots (QDs), surface-engineered with multifunctional polymer ligands that are compact and readily compatible with strain-promoted click conjugation, and the use of these nanocrystals in immunofluorescence and in vivo imaging. The ligand design combines the benefits of mixed coordination (i.e., thiol and imidazole) with zwitterion motifs, yielding sterically-stabilized QDs that present a controllable number of azide groups, for easy conjugation to biomolecules via the selective click chemistry. The polymer coating was characterized using NMR spectroscopy to extract estimates of the diffusion coefficient, hydrodynamic size, and ligand density. The azide-functionalized QDs were conjugated to anti-tropomyosin receptor kinase B antibody (α-TrkB) or to the brain-derived neurotrophic factor (BDNF). These conjugates were highly effective for labeling the tropomyosin receptor kinase B (TrkB) in pyramidal neurons within cortical tissue and for monitoring the BDNF induced activation of TrkB signaling in live neuronal cells. Finally, the polymer-coated QDs were applied for in vivo imaging of Drosophila melanogaster embryos, where the QDs remained highly fluorescent and colloidally stable, with no measurable cytotoxicity. These materials would be of great use in various imaging applications, where a small size, ease of conjugation, and great colloidal stability for in vivo studies are needed.

Modification of Poly(maleic anhydride)-Based Polymers with H2N-R Nucleophiles: Addition or Substitution Reaction?

Reacting poly(maleic anhydride)-based polymers with H2N-R nucleophiles is a flexible and highly effective approach for preparing a variety of multifunctional, multicoordinating, and multireactive polymers. The exact transformation of the anhydride ring during this addition reaction is still an open question. In this report, we characterize the transformation of a representative block copolymer, poly(isobutylene- alt-maleic anhydride), with a few H2N-R nucleophiles. In particular, we test the effects of varying a few reaction parameters/conditions (e.g., temperature, solvent, reaction time, and addition of thionyl chloride) on the nature of the anhydride transformation and bond formed between the polymer and the lateral R groups. The resulting polymers are characterized using a combination of analytical techniques including FT-IR, one- and two-dimensional NMR, and gel electrophoresis. We find that the ring opening transformation occurs under mild conditions. Conversely, cyclic imide transformation can take place for reactions carried out at high temperature (e.g., in DMF under refluxing conditions). We also find that use of a protic solvent, such as methanol, or addition of thionyl chloride (SOCl2) to the reaction mixture under refluxing conditions can promote cyclic imide transformation. The cyclic imide transformation is nonetheless partial, as carboxyl groups could still be accounted for in the resulting compounds. Depending on the type of transformation, the resulting polymer can exhibit a few distinct properties, such as net charge buildup along the chain, or the appearance of weak UV-vis absorption and fluorescence properties. These findings are useful for understanding the properties exhibited by polymer materials prepared via this flexible and highly effective route using anhydride containing polymers and oligomers.

Analysis of risk factors causing short-term cement leakages and long-term complications after percutaneous kyphoplasty for osteoporotic vertebral compression fractures.

Background Percutaneous kyphoplasty (PKP) is a common treatment modality for painful osteoporotic vertebral compression fractures (OVCFs). Pre- and postoperative identification of risk factors for cement leakage and follow-up complications would therefore be helpful but has not been systematically investigated. Purpose To evaluate pre- and postoperative risk factors for the occurrence of short-term cement leakages and long-term complications after PKP for OVCFs. Material and Methods A total of 283 vertebrae with PKP in 239 patients were investigated. Possible risk factors causing cement leakage and complications during follow-up periods were retrospectively assessed using multivariate analysis. Cement leakage in general, three fundamental leakage types, and complications during follow-up period were directly identified through postoperative computed tomography (CT). Results Generally, the presence of cortical disruption ( P = 0.001), large volume of cement ( P = 0.012), and low bone mineral density (BMD) ( P = 0.002) were three strong predictors for cement leakage. While the presence of intravertebral cleft and Schmorl nodes ( P = 0.045 and 0.025, respectively) were respectively identified as additional risk factors for paravertebral and intradiscal subtype of cortical (C-type) leakages. In terms of follow-up complications, occurrence of cortical leakage was a strong risk factor both for new VCFs ( P = 0.043) and for recompression ( P = 0.004). Conclusion The presence of cortical disruption, large volume of cement, and low BMD of treated level are general but strong predictors for cement leakage. The presence of intravertebral cleft and Schmorl nodes are additional risk factors for cortical leakage. During follow-up, the occurrence of C-type leakage is a strong risk factor, for both new VCFs and recompression.

Multifunctional and High Affinity Polymer Ligand that Provides Bio-Orthogonal Coating of Quantum Dots.

We detail the design of hydrophilic metal-coordinating ligands and their use for the effective coating of luminescent quantum dots (QDs). The ligand design exploits the specific, reagent-free nucleophilic addition reaction of amine-modified molecules toward maleic anhydride to introduce several lipoic acid metal anchors, hydrophilic zwitterion moieties, and specific reactive groups along a poly(isobutylene-alt-maleic anhydride) (PIMA) chain. Tunable reactive groups tested in this study include azide, biotin, carboxyl, and amine. Cap exchange with these multilipoic acid ligands via a photochemical ligation strategy yields homogeneous QD dispersions that are colloidally stable over several biologically relevant conditions and for extended periods of time. The zwitterionic coating yields compact nanoparticle size and imparts nonsticky surface properties onto the QDs, preventing protein absorption. The introduction of a controllable number of reactive groups allows conjugation of the QDs to biomolecules via bio-orthogonal coupling chemistries including (1) attachment of the neurotransmitter dopamine to QDs via amine-isothiocyanate reaction to produce a platform capable of probing interactions with cysteine in proteins, based on charge transfer interactions; (2) self-assembly of biotinylated QDs with streptavidin-dye; and (3) ligation of azide-functionalized QDs to cyclooctyne-modified transferrin via copper-free click chemistry, used for intracellular delivery. This ligand design strategy can be used to prepare an array of metal-coordinating ligands adapted for coating other inorganic nanoparticles, including magnetic and plasmonic nanomaterials.

Polydopamine assisted fabrication of titanium oxide nanoparticles modified column for proteins separation by capillary electrochromatography.

Development of a simple method for preparation of stable open tubular (OT) columns for proteins separation by capillary electrochromatography is still challenging. In this work, the titanium oxide (TiO2) nanoparticles coated OT column was successfully prepared for separation of proteins by capillary electrochromatography. The polydopamine (PDA) film was first formed in the inner surface of a fused-silica capillary by the self-polymerization of dopamine under alkaline conditions. Then the TiO2 coating was deposited onto the surface of pre-modified capillary with PDA by a liquid phase deposition process. The plentifully active hydroxyl groups in PDA coating can chelate with Ti(4+) to boost the nucleation and growth of TiO2 film. The as-prepared TiO2 coated OT column was characterized by scanning electron microscopy and measurement of electroosmotic flow. Furthermore, the influence of liquid phase deposition time on the TiO2 coating was investigated. The TiO2 coated OT column was used for successful separation of two variants of ß-lactoglobulin and eight glycoisoforms of ovalbumin. The column demonstrated good repeatability and stability. The relative standard deviations of migration times of proteins representing run-to-run, day-to-day, and column-to-column were less than 3.7%. Moreover, the application of the column was verified by successful separation of acidic proteins in egg white.

Strategies for interfacing inorganic nanocrystals with biological systems based on polymer-coating.

Interfacing inorganic nanoparticles and biological systems with the aim of developing novel imaging and sensing platforms has generated great interest and much activity. However, the effectiveness of this approach hinges on the ability of the surface ligands to promote water-dispersion of the nanoparticles with long term colloidal stability in buffer media. These surface ligands protect the nanostructures from the harsh biological environment, while allowing coupling to target molecules, which can be biological in nature (e.g., proteins and peptides) or exhibit specific photo-physical characteristics (e.g., a dye or a redox-active molecule). Amphiphilic block polymers have provided researchers with versatile molecular platforms with tunable size, composition and chemical properties. Hence, several groups have developed a wide range of polymers as ligands or micelle capsules to promote the transfer of a variety of inorganic nanomaterials to buffer media (including magnetic nanoparticles and semiconductor nanocrystals) and render them biocompatible. In this review, we first summarize the established synthetic routes to grow high quality nanocrystals of semiconductors, metals and metal oxides. We then provide a critical evaluation of the recent developments in the design, optimization and use of various amphiphilic copolymers to surface functionalize the above nanocrystals, along with the strategies used to conjugate them to target biomolecules. We finally conclude by providing a summary of the most promising applications of these polymer-coated inorganic platforms in sensor design, and imaging of cells and tissues.

A multifunctional polymer combining the imidazole and zwitterion motifs as a biocompatible compact coating for quantum dots.

We introduce a set of multicoordinating imidazole- and zwitterion-based ligands suited for surface functionalization of quantum dots (QDs). The polymeric ligands are built using a one-step nucleophilic addition reaction between poly(isobutylene-alt-maleic anhydride) and distinct amine-containing functionalities. This has allowed us to introduce several imidazole anchoring groups along the polymer chain for tight coordination to the QD surface and a controllable number of zwitterion moieties for water solubilization. It has also permitted the introduction of reactive and biomolecular groups for further conjugation and targeting. The QDs capped with these new ligands exhibit excellent long-term colloidal stability over a broad range of pH, toward excess electrolyte, in cell-growth media, and in the presence of natural reducing agents such as glutathione. These QDs are also resistant to the oxidizing agent H2O2. More importantly, by the use of zwitterion moieties as the hydrophilic block, this polymer design provides QDs with a thin coating and compact overall dimensions. These QDs are easily self-assembled with full size proteins expressed with a polyhistidine tag via metal-histidine coordination. Additionally, the incorporation of amine groups allows covalent coupling of the QDs to the neurotransmitter dopamine. This yields redox-active QD platforms that can be used to track pH changes and detect Fe ions and cysteine through charge-transfer interactions. Finally, we found that QDs cap-exchanged with folic acid-functionalized ligands could effectively target cancer cells, where folate-receptor-mediated endocytosis of QDs into living cells was time- and concentration-dependent.

Photoligation of an amphiphilic polymer with mixed coordination provides compact and reactive quantum dots.

We introduce a new set of multicoordinating polymers as ligands that combine two distinct metal-chelating groups, lipoic acid and imidazole, for the surface functionalization of QDs. These ligands combine the benefits of thiol and imidazole coordination to reduce issues of thiol oxidation and weak binding affinity of imidazole. The ligand design relies on the introduction of controllable numbers of lipoic acid and histamine anchors, along with hydrophilic moieties and reactive functionalities, onto a poly(isobutylene-alt-maleic anhydride) chain via a one-step nucleophilic addition reaction. We further demonstrate that this design is fully compatible with a novel and mild photoligation strategy to promote the in situ ligand exchange and phase transfer of hydrophobic QDs to aqueous media under borohydride-free conditions. Ligation with these polymers provides highly fluorescent QDs that exhibit great long-term colloidal stability over a wide range of conditions, including a broad pH range (3-13), storage at nanomolar concentration, under ambient conditions, in 100% growth media, and in the presence of competing agents with strong reducing property. We further show that incorporating reactive groups in the ligands permits covalent conjugation of fluorescent dye and redox-active dopamine to the QDs, producing fluorescent platforms where emission is controlled/tuned by Förster Resonance Energy Transfer (FRET) or pH-dependent charge transfer (CT) interactions. Finally, the polymer-coated QDs have been coupled to cell-penetrating peptides to facilitate intracellular uptake, while subsequent cytotoxicity tests show no apparent decrease in cell viability.

Effects of separation distance on the charge transfer interactions in quantum dot-dopamine assemblies.

We explored the effects of changing the separation distance on the charge transfer interactions between luminescent QD and proximal dopamine (in QD-dopamine assemblies), and the ensuing photoluminescence (PL) quenching. The separation distance was controlled using a tunable size bridge between the QD and dopamine via a poly(ethylene glycol) (PEG) chain where the average number of monomers was discretely varied. Using steady-state and time-resolved fluorescence measurements, we found that the photoluminescence losses were substantially more pronounced for QD-dopamine complexes prepared with the shortest PEG bridge, but progressively decreased with increasing PEG size. We also found that the charge transfer interactions can be affected by the nature of the capping ligand used. In particular, we found that interactions and PL quenching in these assemblies tracked the effects of separation distance, conjugate valence and the energy mismatch between the dopamine redox levels and QD energy levels, when a compact zwitterion was used to control the conjugate configuration. However, additional effects of shielding the access of reactive dopamine to amine groups on the QD surface, when a longer inert PEG ligand was used, were found to produce heterogeneous conjugates, alter the interactions and produce weaker PL quenching.

Polydopamine-coated open tubular column for the separation of proteins by capillary electrochromatography.

The separation and determination of proteins in food is an important aspect in food industry. Inspired by the self-polymerization of dopamine under alkaline conditions and the natural adhesive properties of polydopamine, in this paper, a simple and economical method was developed for the preparation of polydopamine-coated open tubular column, in which ammonium persulfate was used as the source of oxygen to induce and facilitate the polymerization of dopamine to form polydopamine. In comparison with a naked fused-silica capillary, the direction and magnitude of the electro-osmotic flow of the as-prepared polydopamine-coated open tubular column could be manipulated by varying the pH values of background solutions due to the existence of amine and phenolic hydroxyl groups on polydopamine coating. The surface morphology of the polydopamine-coated open tubular column was studied by scanning electron microscopy, and the thickness of polydopamine coating was 106 nm. The performance of the polydopamine-coated open tubular column was validated by analysis of proteins. The relative standard deviations of migration times of proteins representing run-to-run, day-to-day, and column-to-column were less than 3.5%. In addition, the feasibility of the polydopamine-coated open tubular column for real samples was verified by the separation of proteins in chicken egg white and pure milk.

Design of a multi-dopamine-modified polymer ligand optimally suited for interfacing magnetic nanoparticles with biological systems.

We have designed a set of multifunctional and multicoordinating polymer ligands that are optimally suited for surface functionalizing iron oxide and potentially other magnetic nanoparticles (NPs) and promoting their integration into biological systems. The amphiphilic polymers are prepared by coupling (via nucleophilic addition) several amine-terminated dopamine anchoring groups, poly(ethylene glycol) moieties, and reactive groups onto a poly(isobutylene-alt-maleic anhydride) (PIMA) chain. This design greatly benefits from the highly efficient and reagent-free one-step reaction of maleic anhydride groups with amine-containing molecules. The availability of several dopamine groups in the same ligand greatly enhances the ligand affinity, via multiple coordination, to the magnetic NPs, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation with target biomolecules. Iron oxide nanoparticles ligand exchanged with these polymer ligands have a compact hydrodynamic size and exhibit enhanced long-term colloidal stability over the pH range of 4-12 and in the presence of excess electrolytes. Nanoparticles ligated with terminally reactive polymers have been easily coupled to target dyes and tested in live cell imaging with no measurable cytotoxicity. Finally, the resulting hydrophilic nanoparticles exhibit large and size-dependent r2 relaxivity values.

Starch as a smart, cheap, and green gatekeeper for the controlled release of propyl gallate from antioxidant biodegradable packaging films.

Oxidative rancidity of food products and massive consumption of plastic packaging have put the necessity in manufacturing novel antioxidant biodegradable packaging films. A comprehensive investigation was conducted on starch/poly(butylene adipate-co-terephthalate) (PBAT) antioxidant blown films, in which starch acted as a gatekeeper for the controlled release of propyl gallate (PG). PG was well integrated into the matrices and bound to starch molecules by hydrogen bonding. All films showed strong anti-ultraviolet performance, and higher oxygen barrier than the traditional polyethylene film. Increasing starch proportions promoted the swelling of films and the release of PG, thereby causing higher antioxidant activity at the same contact time to free radical solutions. Similar polarity made PG prone to partition and rapid migration into the food simulants with higher ethanol concentration and the high-fat-content peanut butter. The film with 20:80 w/w starch/PBAT proportion and 3% w/w PG content effectively suppressed the oxidation of peanut butter within 300-day storage. Findings demonstrated this strategy for manufacturing starch/PBAT antioxidant films as a long-term active packaging in food industry.

Nonconjugated amylopectin-grafted copolymers with dual fluorescence/low-temperature phosphorescence emission and superior processability.

Nonconjugated fluorescent polymers devoid of large π-π conjugated structures have received considerable attention due to their significant academic importance and broad application potentials in various fields. Herein, we report an effective strategy to fabricate multifunctional fluorescent amylopectin derivatives and reveal their unique aspects of aggregation-induced emission (AIE), cryogenic long-persistent phosphorescence (~6 s) and excellent processabilities characteristics, which are extremely different from traditional luminogens. These amylopectin-graft-poly(n-butyl acrylate-co-1-vinylimidazole) copolymers (Amylopectin-BVs) prepared by the grafting-from method employing RAFT and experienced subsequently with metal-ligand cross-linking. Specifically, clustering-triggered fluorescent emission or cryogenic long-persistent phosphorescence of amylopectin could be achieved by the aggregation of oxygen and nitrogen atoms along with conformation rigidification, which shows great promise in optoelectronic and biological applications.

A biodegradable pH-response packaging film with blueberry extract: Blown-extrusion fabrication, multifunctional activity, and kinetic investigation.

This work proposed a novel strategy for manufacturing biodegradable pH-response packaging. Briefly, to minimize the amount and thermal processing times of blueberry extract (BE), ethanol-dissolved BE (≤ 3‰ w/w) was sprayed onto the starch/poly(butylene adipate-co-terephthalate) (PBAT) pellets before extrusion blowing. BE was well-integrated into the matrix, forming uniformly colored films. The films with BE exhibited superior mechanical (7.85 MPa of strength, 606.53% of elongation) and enhanced barrier capabilities against ultraviolet light, moisture, and gas. Additionally, they exhibited good antioxidant capacity (68.69%), antibacterial activity (72.40%), and maintained color stability. The film with 3‰ w/w BE presented excellent color responsiveness (ΔE⁎ ≥ 15) in the alkaline range, and successfully monitored the spoilage of shrimp. The pigments in the film had the maximum migration degree (≥ 70%) and rate in 50% ethanol simulation, following a first-order kinetic behavior dominated by Fickian diffusion. Findings supported the application of this strategy in the fabrication of starch/PBAT/BE films for pH-response intelligent packaging.

Effects of starch filling on physicochemical properties, functional activities, and release characteristics of PBAT-based biodegradable active films loaded with tea polyphenols.

In this work, the modification of poly(butylene adipate-co-terephthalate) (PBAT) was combined with the development of active packaging films. PBAT, starch, plasticizer, and tea polyphenols (TP) were compounded and extrusion-blown into thermoplastic starch (TPS)/PBAT-TP active films. Effects of TPS contents on physicochemical properties, functional activities, biodegradability, and release kinetics of PBAT-based active films were explored. Starch interacted strongly with TP through hydrogen bonding and induced the formation of heterogeneous structures in the films. With the increase in TPS contents, surface hydrophilicity and water vapor permeability of the films increased, while mechanical properties decreased. Blending starch with PBAT greatly accelerated degradation behavior of the films, and the T30P70-TP film achieved complete degradation after 180 days. As TPS contents increased, swelling degree of the films increased and TP release were improved accordingly, resulting in significantly enhanced antioxidant and antimicrobial activities. This work demonstrated that filling starch into PBAT-based active films could achieve different antioxidant and antimicrobial activities of the films by regulating film swelling and release behavior.

Water-resistant and pyknotic recyclable waste-cotton-derived bio-polyurethane-coated controlled-release fertilizer: Improved longevity, mechanism and application.

Reasonably utilize the recyclable waste-cotton resource to develop the bio-polyurethane coatings had aroused more and more environmental interests recently. However, the terrible water resistance and porousness of the waste-cotton-derived bio-polyurethane coating caused the rapid nutrients release. In this work, the water-resistant and pyknotic cotton-fibre-derived coated-ureas (WPCUs) were fabricated with the recyclable low-cost waste-cotton-derived materials. The dramatically enhanced pyknotic and water-resistant characteristics of the WPCUs coatings can be obtained by the three-dimensional computerized tomography (2.33 to 1.19 %) and the water contact angle. The enhanced elasticity and the decreased water absorption were also vital to enhance the controlled-release performance. The accompanying controlled-release performance of the WPCUs was obviously improved (<2 h to 58.43 days). The modified WPCU75-10 with 4.0 % coating content exhibits the excellent controlled-release performance compared to the unmodified WPCU0-0. The controlled release mechanism can be clarified: The air column inside of the "small and few" micropores in the WPCUs coating only allow the gaseous water molecules to slowly penetrate and dissolve the inner urea cores (rather than liquid water). The obviously increased oilseed rape yield (128.75 %) showed the dependable agricultural application of the WPCUs. This work provides the resultful approach to develop the eco-friendly recyclable waste-plant-derived controlled-release fertilizers.

Relationship between phase morphologies and mechanical properties of thermoplastic starch/poly(butylene adipate-co-terephthalate) composite films prepared by extrusion blowing.

Biodegradable films with various weight proportions of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate) (PBAT) were prepared by extrusion blowing. Relationship between phase morphologies and mechanical properties of TPS/PBAT composite films was investigated and discussed. Iodine dyeing technique was used to clearly identify TPS and PBAT phases in the composite films. Such blending systems proved to be immiscible and the phase morphology evolution with changes in TPS/PBAT proportions was elucidated. Two phase transition points were found near PBAT content of 30 and 70 wt%, respectively, where mechanical properties of the composite films leaped. Significant correlations were established between mechanical properties and continuity indices of the two phases, namely a positive correlation with continuity index of PBAT and a negative correlation with that of TPS. Inducing the formation and enhancement of continuous structure of PBAT phase is proposed as a practical approach to improve mechanical properties of TPS/PBAT composite films.