Petal-like Patterning of Polylactide/Poly (Butylene Succinate) Thin Films Induced by Phase Separation.

Biodegradable plastics are attracting attention as a solution to the problems caused by plastic waste. Among biodegradable plastics, polylactide (PLA) and poly (butylene succinate) (PBS) are particularly noteworthy because of their excellent biodegradability. However, the drawbacks of their mechanical properties prompts the need to compound them to achieve the desired strength. The characteristics of the interface of the composite material determine the realization of its final performance. The study of the interface and microstructure of composites is essential for the development of products from degradable polymers. The morphology evolution and microcrystal structure of spin-casted fully biodegradable (PLA/PBS) blend films were investigated using atomic force microscopy (AFM)-based nanomechanical mapping. Results show that intact blend films present an obvious phase separation, where the PBS phase is uniformly dispersed in the PLA phase in the form of pores. Furthermore, the size and number of the PBS phase have a power exponential relationship and linear relationship with PBS loading, respectively. Intriguingly, after annealing at 80 °C for 30 min, the PLA phase formed an orderly petal-like microcrystalline structure centered on the PBS phase. Moreover, the microcrystalline morphology changed from a "daisy type" to a "sunflower type" with the increased size of the PBS phase. Since the size of the PBS phase is controllable, a new method for preparing microscopic patterns using fully biodegradable polymers is proposed.

Colorless, Transparent, and High-Performance Polyurethane with Intrinsic Ultraviolet Resistance and Its Anti-UV Mechanism.

Polyurethane (PU) is a widely used polymer material that will age under prolonged exposure to ultraviolet (UV) light, shortening the service life. Several methods have been used to prepare the anti-UV PU, including adding nonreactive anti-UV additives, functional fillers, and biological antioxidant molecules. However, the nonreactive anti-UV additives may migrate during long-term use, the functional fillers may damage the mechanical properties and seriously reduce the light transmittance of the sample, and the biological antioxidant molecules will inevitably color the sample. To solve these problems, in this work, a benzotriazole UV absorber (Chiguard R-455) was introduced into the PU molecular chains by in situ polymerization to prepare the nonmigrating intrinsic anti-UV PU sample with high performance and colorless transparency. The anti-UV PU samples exhibit light transmittance of over 88% in the visible range and superior mechanical properties with tensile strength higher than 65 MPa and elongation at break higher than 900%. After 24 h UV irradiation (200 W, 365 nm), the tensile strength and elongation at break of pure PU sample are significantly reduced to only 8.9 and 15.8% of the original one, respectively. On the contrary, the addition of Chiguard R-455 will endow the PU sample with excellent anti-UV performance. After 24 h UV irradiation, the tensile strength (67.2 ± 1.6 MPa) and elongation at break (917.4 ± 30.0%) of PU-0.5% (the content of Chiguard R-455 is only 0.5 wt %) have changed little compared with the sample without irradiation (67.4 ± 3.5 MPa and 919.4 ± 26.5%). Additionally, the anti-UV mechanism of the PU sample is systematically studied. This work provides a feasible method for preparing colorless, transparent, high-performance, nonmigrating intrinsic UV-shielding PU samples, which can be used as a UV light-shielding material in various fields with visible and aesthetic requirements, such as protection fields and wearable products.

Thermal/Near-Infrared Light Dual-Responsive Reconfigurable and Recyclable Polythiourethane/CNT Composite with Simultaneously Enhanced Strength and Toughness.

Thermoset polymers cross-linked by dynamic covalent bonds are recyclable and reconfigurable based on solid-state plasticity, resulting in less waste and environmental pollution. However, most thermoset polymers previously reported show thermal-responsive solid-state plasticity, depending much on external conditions and not allowing for local shape modulation. Herein, the isocyanate modified carbon nanotubes (CNTs-NCO) are introduced into the polythiourethane (PCTU) network with multiple dynamic covalent bonds by in situ polymerization to prepare the composite with thermal/light dual-responsive solid-state plasticity, reconfigurability, and recyclability. The introduction of CNTs-NCO simultaneously strengthens and toughens the PCTU composite. Moreover, based on the photothermal properties and light-responsive solid-state plasticity, the PCTU/CNTs composite or bilayer sample can achieve complex permanent shape by locally precise shape regulation without affecting other parts. This work provides a simple and reliable method for preparing high-performance polymer composite with light-responsive solid-state plasticity, which may be applied in the fields of sensing and flexible electronics.

Dual pH-Responsive and Tumor-Targeted Nanoparticle-Mediated Anti-Angiogenesis siRNA Delivery for Tumor Treatment.

Purpose: In order to overcome the biological barriers at all levels and enhance the delivery efficiency of siRNA, we have prepared a multifunctional siRNA delivery system (CHCE/siRNA nanoparticles) through self-assembly of the carboxymethyl chitosan modified with histidine, cholesterol, and anti-EGFR antibody (CHCE). Methods: The morphology of CHCE/siRNA NPs was detected by dynamic light scattering and scanning electron microscope. In vitro, we assessed the tumor-targeting, cellular uptake, and endosomal escape by flow cytometry and confocal laser scanning microscopy, confirming the CHCE/siRNA NPs functions in gene silencing and cell killing ability. In vivo, we examined the biodistribution of the CHCE/siRNA NPs by the IVIS imaging system and confirmed the therapeutic effect of NPs in the nude-mouse tumor model. Results: The CHCE/siRNA NPs exhibited nanosized spherical with narrow size distribution. In vitro, the CHCE/siRNA NPs incorporated a dual capability of tumor targeting and pH response that could facilitate cellular bind, cellular uptake, and endosomal escape. The CHCE/siRNA NPs could effectively silence the vascular endothelial growth factor A (VEGFA) to cause cell apoptosis and inhibit proliferation. In vivo, the CHCE/siRNA NPs could target tumor sites to knock down VEGFA and achieve a better anti-tumor effect. Conclusion: We successfully prepared a novel siRNA delivery system with the double capability of tumor targeting and pH response, which can break through the biological barriers to penetrate deep into tumors and achieve better therapeutic tumor effects, providing a new ideal delivery platform for siRNA.

Multifunctional nanoparticles co-loaded with Adriamycin and MDR-targeting siRNAs for treatment of chemotherapy-resistant esophageal cancer.

The development of multidrug resistance (MDR) during cancer chemotherapy is a major challenge in current cancer treatment strategies. Numerous molecular mechanisms, including increased drug efflux, evasion of drug-induced apoptosis, and activation of DNA repair mechanisms, can drive chemotherapy resistance. Here we have identified the major vault protein (MVP) and the B-cell lymphoma-2 (BCL2) gene as two potential factors driving MDR in esophageal squamous cell carcinoma (ESCC). We have designed a novel and versatile self-assembling nanoparticle (NP) platform on a multifunctional carboxymethyl chitosan base to simultaneously deliver Adriamycin, and siRNAs targeting MVP and BCL2 (CEAMB NPs), thus reducing drug efflux and promoting apoptosis of esophageal cancer cells. To achieve effective delivery to tumor tissues and inhibit tumor growth in vivo, carboxymethyl chitosan was engineered to contain multiple histidines for enhanced cytosol delivery, cholesterol for improved self-assembly, and epidermal growth factor receptor (EGFR) antibodies to target cancer cells. Our results indicate that these nanoparticles are efficiently synthesized with the desired chemical composition to self-assemble into cargo-containing NPs. Furthermore, we have shown that the synthesized NPs will successfully inhibit cancer cells growth and tumor development when delivered to cultured ESCC cells or to in vivo mouse xenograft models. Our engineered NPs offer a potential novel platform in treating various types of chemotherapy-resistant tumors.

Arbitrarily Reconfigurable and Thermadapt Reversible Two-Way Shape Memory Poly(thiourethane) Accomplished by Multiple Dynamic Covalent Bonds.

The fabrication of a single polymer network that exhibits a good reversible two-way shape memory effect (2W-SME), can be formed into arbitrarily complex three-dimensional (3D) shapes, and is recyclable remains a challenge. Herein, we design and fabricate poly(thiourethane) (PTU) networks with an excellent thermadapt reversible 2W-SME, arbitrary reconfigurability, and good recyclability via the synergistic effects of multiple dynamic covalent bonds (i.e., ester, urethane, and thiourethane bonds). The PTU samples with good mechanical performance simultaneously demonstrate a maximum tensile stress of 29.7 ± 1.1 MPa and a high strain of 474.8 ± 7.5%. In addition, the fraction of reversible strain of the PTU with 20 wt % hard segment reaches 22.4% during the reversible 2W-SME, where the fraction of reversible strain is enhanced by self-nucleated crystallization of the PTU. A sample with arbitrarily complex permanent 3D shapes can be realized via the solid-state plasticity, and that sample also exhibits excellent reversible 2W-SME. A smart light-responsive actuator with a double control switch is fabricated using a reversible two-way shape memory PTU/MXene film. In addition, the PTU networks are de-cross-linked by alcohol solvolysis, enabling the recovery of monomers and the realization of recyclability. Therefore, the present study involving the design and fabrication of a PTU network for potential applications in intelligent actuators and multifunctional shape-shifting devices provides a new strategy for the development of thermadapt reversible two-way shape memory polymers.

Thermal/Near-Infrared Light Dual-Responsive Reversible Two-Way Shape Memory cEVA/2D-MoO2 Composite for Multifunctional Applications.

Light-responsive reversible two-way shape memory polymers (2W-SMPs) are highly promising for many fields due to indirect heating, clean, and remote control. In this work, a composite with both thermal- and near-infrared (NIR) light-induced reversible two-way shape memory effect (2W-SME) is prepared by doping extremely little quantities of 2D non-layered molybdenum dioxide nanosheets (2D-MoO2 ) into semicrystalline poly(ethylene-co-vinyl acetate) (EVA) networks. This is the first report on light-induced reversible two-way shape memory composites employing 2D-MoO2 as photothermal fillers. Upon switching the NIR light on and off, due to the excellent photothermal feature and stability of 2D-MoO2 , the composite exhibits remarkable light-induced reversible 2W-SME. A light-driven actuator for sensing applications is designed based on the composite and the circuit, where the lamp acting as an alarm can raise and fade upon responding to NIR light. A completely flexible, fuel-free self-walking soft robot is designed based on the advantages of the light-responsive reversible 2W-SMPs. Additionally, the composite acting as a light-fueled crane is able to lift and lower a load that is 3846 times its own weight. The results demonstrate that the prepared composite has a promising prospect for applications as actuators, self-walking soft robot and crane.

Cascade-Targeting of Charge-Reversal and Disulfide Bonds Shielding for Efficient DOX Delivery of Multistage Sensitive MSNs-COS-SS-CMC.

BACKGROUND: Although pH and redox sensitiveness have been extensively investigated to improve therapeutic efficiency, the effect of disulfide bonds location and pH-triggered charge-reversal on cascade-targeting still need to be further evaluated in cancer treatment with multi-responsive nanoparticles. PURPOSE: The aim of this study was to design multi-responsive DOX@MSNs-COS-NN-CMC, DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS and systematically investigate the effects of disulfide bonds location and charge-reversal on the cancer cell specificity, endocytosis mechanisms and antitumor efficiency. RESULTS: In vitro drug release rate of DOX@MSNs-COS-SS-CMC in tumor environments was 7-fold higher than that under normal physiological conditions after 200 h. Furthermore, the fluorescence intensity of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS was 1.9-fold and 1.3-fold higher than free DOX at pH 6.5 and 10 mM GSH. In addition, vesicular transport might be a factor that affects the uptake efficiency of DOX@MSNs-COS-SS-CMC and DOX@MSNs-COS-CMC-SS. The clathrin-mediated endocytosis and endosomal escape of DOX@MSNs-COS-SS-CMC enhanced cellular internalization and preserved highly controllable drug release into the perinuclear of HeLa cells. DOX@MSNs-COS-SS-CMC exhibited a synergistic chemotherapy in preeminent tumor inhibition and less side effects of cardiotoxicity. CONCLUSION: The cascade-targeting of charge-reversal and disulfide bonds shielding would be a highly personalized strategy for cervical cancer treatment.

Morphology and transport characterization of solution-processed rubrene thin films on polymer-modified substrates.

In this report, the morpho-structural peculiarities and the crystallization mechanisms in solution-processed, solvent vapor annealed (SVA) thin films of rubrene (5,6,11,12-tetraphenylnaphthacene) on different substrates were investigated. The high-quality rubrene crystal films with a triclinic crystal structure were successfully prepared on the FTO substrates (glass slide coated with fluorine-tin-oxide) modified by PLA (polylactic acid) for the first time. The area coverage of rubrene crystal and the sizes of rubrene dendritic crystals increased with increasing thickness of PLA film and concentration of rubrene solution. For rubrene molecules, FTO wafers with rough surface provided the possibility of heterogeneous nucleation. During the SVA process, there were two kinds of forces acting on the diffusion of rubrene molecules: one force was provided by the residual chloroform solvent, which was perpendicular to the substrate, and the other force was provided by gaseous dichloromethane, which was parallel to the substrate. The synergy of these two forces was proposed to explain the nucleation and the crystallization processes of rubrene films. The higher nucleus of PLA/rubrene dendrites and the layer-by-layer stacking of needle-shaped nanocrystalline PLA/rubrene were important for exploring their kinetic formation process.

The Thermal Behavior of γ-PA1010: Evolution of Structure and Morphology in the Simultaneous Thermal Stretched Films.

In this work, polyamide 1010 (PA1010) films were prepared by melt-quenching. A wide-angle X-ray diffractometer (WAXD) with a thermal stretching stage was used to investigate the structure transformation, crystallinity and degree of orientation in the course of simultaneous thermally stretched PA1010. The crystallinity increased along with the increase of draw ratio and then decreased as the draw ratio was over 2.00 times-which the maximum value reached when the draw ratio was about 2.00 times. The degree of orientation of γ-PA1010 was much greater at higher temperature than room temperature (RT); the difference gradually became weaker with the increase of draw ratio. There was a linear relationship between the draw ratios and tensile force at higher temperatures, and the tensile force increased with the increase of draw ratios. The tensile force may induce crystallization and promote orientation in the course of simultaneous thermally stretched PA1010. These phenomena are beneficial to understand the structure-processing-performance relationship and provide some theoretical basis for the processing and production.

Cell Type-Dependent Specificity and Anti-Inflammatory Effects of Charge-Reversible MSNs-COS-CMC for Targeted Drug Delivery in Cervical Carcinoma.

The surface charge of nanocarriers inevitably affects drug delivery efficiency; however, the cancer cell specificity, anti-inflammatory effects, and charge-reversal points remain to be further addressed in biomedical applications. The aim of this study was to comprehensively assess the cancer cell specificity of DOX-loaded mesoporous silica-chitosan oligosaccharide-carboxymethyl chitosan nanoparticles (DOX@MSNs-COS-CMC) in MCF-7 and HeLa cells, inhibit the production of inflammatory cytokines, and improve the drug accumulation in the tumor site. Intracellular results reveal that the retention time prolonged to 48 h in both HeLa and MCF-7 cells at pH 7.4. However, DOX@MSNs-COS-CMC exhibited a cell type-dependent cytotoxicity and enhanced intracellular uptake in HeLa cells at pH 6.5, due to the clathrin-mediated endocytosis and macropinocytosis in HeLa cells in comparison with the vesicular transport in MCF-7 cells. Moreover, Pearson's correlation coefficient value significantly decreased to 0.25 after 8 h, prompting endosomal escape and drug delivery into the HeLa nucleus. After the treatment of MSNs-COS-CMC at 200 µg/mL, the inflammatory cytokines IL-6 and TNF-α level decreased by 70% and 80%, respectively. Tumor inhibition of DOX@MSNs-COS-CMC was 0.4 times higher than free DOX, alleviating cardiotoxicity and inflammation in the HeLa xenograft tumor model. Charge-reversible DOX@MSNs-COS-CMC could be a possible candidate for clinical therapy of cervical carcinoma.

A DFT study on the photoelectric properties of rubrene and its derivatives.

The way to obtain new materials was usually to introduce some groups to molecules. Correlations among the molecular structure and photoelectric properties of rubrene and its eight derivatives have been studied in this paper, and the influences of the introduction of different electron-donating and withdrawing substituents on the molecular orbital, reorganization energies, absorption spectra, and fluorescence spectra of rubrene and its derivatives were discussed. In the present work, density functional theory calculations were performed at the B3LYP/6-311G(d,p) level to optimize the structure, and TD-DFT was used to calculate the absorption and emission spectra. Quantum chemistry calculation results indicated that the maximum absorption wavelengths are redshifted due to the introduction of cyclopentadienyl or furan groups, the maximum absorption wavelengths are blueshifted while methoxy groups substituted on tetracene backbone. We also discussed the influence of substituents on the molecule structure, which suggests that introducing furan and cyclopentadienyl substituents on the tetracene backbone can increase the rigidity of rubrene and improve the fluorescence intensity. The results of reorganization show that the introduction of cyclopentadienyl or furan groups into rubrene is advantageous to the holes transportation, and the introduction of F groups contributes to the electrons transportation. This study provides an insight into the properties of rubrene and its derivatives and supplies an effective method to design new organic semiconductor materials.

Amphiphilic poly(caprolactone-b-N-hydroxyethyl acrylamide) micelles for controlled drug delivery.

To increase the bioavailability and water solubility of hydrophobic medicine, an amphiphilic block copolymer, polycaprolactone-block-polyhydroxyethyl acrylamide (PCL-b-PHEAA), was synthesized. The copolymer can self-assemble into micelles by dialysis. The micelles were characterized by the Tyndall effect, static drop method, fluorescence spectrometry, dynamic light scattering, scanning electron microscopy and transmission electron microscopy. Ibuprofen was encapsulated inside the micelles by dialysis as a model medicine. The results show that the amphiphilic copolymer forms a uniform micelle system, with spherical micelles dispersed well in solution which have a low critical micelle concentration. In addition, the system shows good amphipathic behavior. Average particle size of a micelle is 104 nm, which increases a lot after drug loading and standing for half a month. In the first few hours, the cumulative release of the drug increases gradually; the rate of increase in the first ten hours is faster, then reaching a plateau which tends to be flat finally. It is similar under two different pH conditions. This biocompatible, biodegradable amphiphilic block copolymer has potential applications in the biomedical field.

pH-Triggered Charge-Reversal Mesoporous Silica Nanoparticles Stabilized by Chitosan Oligosaccharide/Carboxymethyl Chitosan Hybrids for Effective Intracellular Delivery of Doxorubicin.

Surface modification of mesoporous silica nanoparticles (MSNs) is a promising way to enhance therapeutic efficacy and minimize side effects of anticancer drugs. In this work, MSNs with reduced particle size and optimum pore diameter were obtained and catalyzed by ammonia/triethanolamine. In view of the negatively charged carboxymethyl chitosan (CMC) and positively charged chitosan oligosaccharide (CS), the pH-triggered charge-reversal CS/CMC bilayer was designed as a stimuli-responsive switch for MSNs via the protonation and deprotonation effect. The results showed that MSNs-CS/CMC were core-shell and mesoporous in structure. Surface charge conversion and pH dependence were clearly observed in the doxorubicin hydrochloride (DOX) delivery. The intracellular uptake indicated that DOX@MSNs-CS/CMC could be distributed in the cytoplasm of MCF-7 cells and exhibited lower toxicity, which would improve the stability and prolong the retention time compared to free DOX and unmodified DOX@MSNs at pH 7.4. Moreover, the cellular uptake and internalization of DOX@MSNs-CS/CMC were enhanced to promote drug delivery into the cell nucleus at pH 6.5. The biocompatible and surface-charge-reversible MSNs-CS/CMC have the potential to prolong the retention time in the bloodstream, facilitate the endosome escape, and enrich the targeted antitumor strategy, providing an alternative platform for efficient drug delivery in breast cancer therapy.

Synthesis and structure/properties characterizations of four polyurethane model hard segments.

Four model polyurethane (PU) hard segments were synthesized by reaction of butanol with four typical diisocyanates. The four diisocyanates were aromatic 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and MDI-50 (50% mixture of 2,4'-MDI and 4,4'-MDI), cycloaliphatic 4,4'-dicyclohexylmethane diisocyanate (HMDI) and linear aliphatic 1,6-hexamethylene diisocyanate (HDI). FTIR, 1H NMR, 13C NMR, MS, X-ray and DSC methods were employed to determine their structures and to analyse their crystallization behaviours and hydrogen bonding interactions. Each of the four PU compounds prepared in the present work displays unique spectral characteristics. The FTIR bands and NMR resonance peaks assigned in the four samples thus provide a reliable database and starting point for investigating the relationship between hard segment structure and the crystallization and hydrogen bonding behaviour in more complex-segmented PU compositions.

DNA Hydrogel with Tunable pH-Responsive Properties Produced by Rolling Circle Amplification.

Recently, smart DNA hydrogels, which are generally formed by the self-assembly of oligonucleotides or through the cross-linking of oligonucleotide-polymer hybrids, have attracted tremendous attention. However, the difficulties of fabricating DNA hydrogels limit their practical applications. We report herein a novel method for producing pH-responsive hydrogels by rolling circle amplification (RCA). In this method, pH-sensitive cross-linking sites were introduced into the polymeric DNA chains during DNA synthesis. As the DNA sequence can be precisely defined by its template, the properties of such hydrogels can be finely tuned in a very facile way through template design. We have investigated the process of hydrogel formation and pH-responsiveness to provide rationales for functional hydrogel design based on the RCA reaction.

Comparative study of polymer containing beta-cyclodextrin and -COOH for adsorption toward aniline, 1-naphthylamine and methylene blue.

Three different polymers P1, P2 and P3 (P1 containing both beta-CD and -COOH, P2 containing beta-CD and P3 containing -COOH) were synthesized and applied to adsorption toward aniline, 1-naphthylamine and methylene blue. The concentrations (C) before and after adsorption were determined and the adsorption capacities (q) of P1, P2 and P3 were calculated. The maximum adsorption capacities (q(max)) toward aniline: q(max) (P1)=104 micromol g(-1), q(max) (P2)=14.9 micromol g(-1) and q(max) (P3)=53.1 micromol g(-1); toward 1-naphthylamine: q(max) (P1)=184 micromol g(-1), q(max) (P2)=53.8 micromol g(-1) and q(max) (P3)=125 micromol g(-1); toward methylene blue: q(max) (P1)=200 micromol g(-1), q(max) (P2)=12.7 micromol g(-1) and q(max) (P3)=215 micromol g(-1). P1 exhibited remarkable adsorption toward all the three adsorbates. P2 was almost equal to P1 in adsorption toward methylene blue, but was less efficient than P1 in adsorption toward aniline and 1-naphthylamine. P3 also exhibited considerable adsorption toward aniline and 1-naphthylamine, but was inefficient toward methylene blue. P1 was obtained from nontoxic materials and through environment friendly procedures, so it was potentially an efficient and green adsorbent for water purification.

FTIR spectroscopic characterization of polyurethane-urea model hard segments (PUUMHS) based on three diamine chain extenders.

Six polyurethane-urea model hard segments (PUUMHS) were prepared by a solution method based, respectively, on two isocyanates: 4,4'-methylene-diphenyl-diisocyanate (MDI), 4,4'-methylene-dicyclohexyl diisocyanate (HMDI) and three amine chain extenders: ethylene diamine (EDA), methylene-bis-ortho-chloroaniline (MOCA), 2,4-diamino-3,5-dimethylsuphylchlorobenzene (DDSCB). FTIR was used to study their spectroscopic characterization. The main FTIR bands of the six samples were assigned and compared. It was found that most of N-H and C=O are H-bonded in these PUUMHS. However, the N-H in three MDI based PUUMHS is all in the stronger H-bond state than that in their corresponding HMDI based while the C=O in three HMDI based PUUMHS is all in the stronger H-bond state than that in their corresponding MDI based, respectively. In addition, the order of the H-bond strength in HMDI based PUUMHS is MOCA, DDSCB and EDA whether according to nuN-H or nuC=O band wavenumbers, which is, however, different from that in MDI based PUUMHS. Moreover, the HMDI based PUUMHS shows obvious double amide III bands while the MDI based has only prominent one. The results are discussed according mainly to the different characteristics of the three chain extenders as well as the structure difference between MDI and HMDI.