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.

Novel Monomethoxy Poly(Ethylene Glycol) Modified Hydroxylated Tung Oil for Drug Delivery.

Novel monomethoxy poly(ethylene glycol) (mPEG) modified hydroxylated tung oil (HTO), denoted as mPEG-HTO-mPEG, was designed and synthesized for drug delivery. mPEG-HTO-mPEG consists of a hydroxylated tung oil center joined by two mPEG blocks via a urethane linkage. The properties of mPEG-HTO-mPEG were affected by the length of the mPEG chain. Three mPEG with different molecular weights were used to prepare mPEG-HTO-mPEG. The obtained three mPEG-HTO-mPEG polymers were characterized by nuclear magnetic resonance (NMR), Fourier transformation infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively. Furthermore, the particle sizes of mPEG-HTO-mPEG micelles were evaluated by dynamic light scattering (DLS) and transmission electron microscope (TEM). A critical aggregation concentration (CAC) ranged from 7.28 to 11.73 mg/L depending on the chain length of mPEG. The drug loading and release behaviors of mPEG-HTO-mPEG were investigated using prednisone acetate as a model drug, and results indicated that hydrophobic prednisone acetate could be effectively loaded into mPEG-HTO-mPEG micelles and exhibited a long-term sustained release. Moreover, compared with HTO, mPEG-HTO-mPEG had no obvious cytotoxicity to HeLa and L929 cells. Therefore, monomethoxy poly(ethylene glycol) modified hydroxylated tung oil mPEG-HTO-mPEG may be a promising drug carrier.

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.

Integrated transcriptomic and metabolomic analyses revealed the regulatory mechanism of sulfur application in grain yield and protein content in wheat (Triticum aestivum L.).

Sulfur fertilizers play an important role in increasing the yield and improving the dough quality of bread wheat, but their regulatory mechanism remains unclear. In this study, 0 kg·ha-1 (S0) and 60 kg·ha-1 (S60) of sulfur were applied on the anthesis date; subsequently, immature wheat grains at 8, 13, and 18 days post-anthesis (DPA) were subjected to integrated transcriptomic and metabolomic analyses to investigate the changes in the gene/metabolite activity in a typical strong-gluten wheat, Gaoyou2018 (GY2018). Our data show that the S60 treatment could significantly increase the grain yield and grain protein content by 13.2 and 3.6%, respectively. The transcriptomic analysis revealed that 10,694 differentially expressed genes (DEGs) were induced by S60 from 8 to 18 DPA when compared with their corresponding no-sulfur controls, and most DEGs were mainly involved in lipid metabolism and amino acid metabolism pathways. Ninety-seven MYB transcription factors (TFs) were identified as responsive to the S60 treatment; of these, 66 showed significantly differential expression at 13 DPA, and MYB118 might participate in the process of sulfur metabolism by regulating glucosinolate synthesis. In total, 542 significantly enriched differentially expressed (DE) metabolites (DEMs) were identified following the S60 treatment, which mainly included secondary metabolites, carbohydrates, and amino acids. Several metabolites (e.g., glutathione, sucrose, GDP-alpha-D-glucose, and amino acids) exhibited altered abundances following the S60 treatment. The combination of transcriptomic and metabolomic analyses highlighted the important role of amino acid metabolism (especially cysteine, methionine, and glutathione metabolism) and starch and sucrose metabolism pathways after S60 application. Our results provide valuable information enhancing our understanding of the molecular mechanism of the response to sulfur and provide useful clues for grain protein quality formation and yield improvement in bread wheat.

Transparent, photothermal and stretchable alginate-based hydrogels for remote actuation and human motion sensing.

Multifunctional hydrogels show potential applications in actuators and wearable sensors. However, it is still a challenge to develop a photothermal responsive conductive hydrogel with high transparency, mechanical properties, broad sensing range, and low-temperature resistance. In this work, a transparent, photothermal responsive, and highly stretchable alginate-based hydrogels was feasibly constructed by adding two-dimensional non-layered molybdenum dioxide nanosheets (2D-MoO2) to sodium alginate/polyacrylamide mixture and then soaking into the calcium chloride solution. The introduction of 2D-MoO2 renders the hydrogels excellent photothermal properties and controllable photomechanical deformation under near-infrared irradiation, while maintaining high transparency (~60 %).The calcium ions give the hydrogel excellent mechanics, conductivity, and freezing tolerance concurrently. The transparent hydrogel-based sensor shows wide sensing range (0-1800 %) and cycling stability in detecting deformations and real-time human motions even in harsh environments. Therefore, this work provides a new route for generating transparent multifunctional hydrogels towards the applications of remote actuation and strain sensing.

Real-time time-optimal continuous multi-axis trajectory planning using the trajectory index coordination method.

Real-time time-optimal trajectory planning exists in a wide range of applications such as computer numerical control (CNC) manufacturing, robotics and autonomous vehicles. Generally, the methods to generate time-optimal trajectory can be categorized as non-real-time methods and real-time methods. Non-real-time methods such as direct optimization method tend to generate time-optimal trajectory through nonlinear or linear programming while it is computationally prohibitive for high frequency real-time applications. Current real-time methods are computationally efficient but either deal with the sparse waypoint trajectories or sacrifice the time optimality a lot. This paper innovatively proposed a time-optimal switching trajectory index coordination (TOS-TIC) framework to solve the real-time time-optimal planning problem for continuous multi-axis trajectories. The proposed method is able to generate time-optimal trajectory for continuous geometric paths while considering the axial velocity and acceleration constraints. The time-optimality of the trajectory planned by TOS-TIC is nearly the same as the offline planned optimal results. Meanwhile, the proposed method is computationally efficient for even 5kHz real-time applications. The main idea of TOS-TIC is coordinating several one-axis time-optimal switching controls to generate a modified control that decreases the state deviation from the desired trajectory. Several comparative experiments are carried out on an industrial biaxial linear motor stage. And the experimental results consistently verify that the proposed TOS-TIC real-time planner generates faster trajectory compared with the real-time lookahead method. In addition, the trajectory running time and final tracking error of the proposed method are nearly the same as the offline direct optimization method.

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.

Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions.

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La0.7 Sr0.3 MnO3-δ epitaxial thin films, both at the surface and throughout the bulk. Using polarized neutron reflectometry, a quantitative depth profile of the oxygen content gradient is achieved, which, alongside atomic-resolution scanning transmission electron microscopy, uniquely reveals the formation of a novel structural phase near the surface. Surface-sensitive X-ray spectroscopies further confirm a significant change of the electronic structure accompanying the transition. The anisotropic features of this novel phase enable a distinct oxygen diffusion pathway in contrast to conventional observation of oxygen motion at moderate temperatures. The results provide insights furthering the design of solid oxygen ion conductors within the framework of topotactic phase transitions.

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.

Rapid Photothermal Responsive Conductive MXene Nanocomposite Hydrogels for Soft Manipulators and Sensitive Strain Sensors.

Stimulus-responsive hydrogels are of great significance in soft robotics, wearable electronic devices, and sensors. Near-infrared (NIR) light is considered an ideal stimulus as it can trigger the response behavior remotely and precisely. In this work, a smart flexible stimuli-responsive hydrogel with excellent photothermal property and decent conductivity are prepared by incorporating MXene nanosheets into the physically cross-linked poly(N-isopropyl acrylamide) hydrogel matrix. Because of outstanding photothermal effect and dispersion of MXene, the composite hydrogel exhibits rapid photothermal responsiveness and excellent photothermal stability under the NIR irradiation. Furthermore, the anisotropic bilayer hydrogel actuator shows fast and controllable light-driven bending behavior, which can be used as a light-controlled soft manipulator. Meanwhile, the hydrogel sensor exhibits cycling stability and good durability in detecting various deformation and real-time human activities. Therefore, the present study involving the fabrication of MXene nanocomposite hydrogels for potential applications in remotely controlled actuator and wearable electronic device provides a new method for the development of photothermal responsive conductive hydrogels.

Two-Dimensional MoO2 Nanosheet Composite Hydrogels with High Transmittance and Excellent Photothermal Property for Near-Infrared Responsive Actuators and Microvalves.

Stimulus-responsive intelligent hydrogel actuators have highly promising applications in the fields of soft robotics, smart manipulators, and flexible devices. Near-infrared (NIR) light is considered an ideal method to trigger the response behavior remotely and precisely. In order to realize the excellent optical transmittance and photothermal property of NIR-responsive hydrogels at the same time, two-dimensional nonlayered MoO2 nanosheets (2D-MoO2) with excellent photothermal efficiency (62% under an NIR light irradiation of 808 nm), splendid chemistry stability, and low preparation cost are used as photothermal agents and incorporated into the poly(N-isopropylacrylamide) (PNIPAM) hydrogel network, forming the 2D-MoO2/Laponite/PNIPAM ternary nanocomposite hydrogel (TN hydrogel). It is remarkable that compared with the GO and MXene hydrogels with the same agent content (1.0 mg mL-1) and thickness (1 mm) whose transmittance values are only ∼5% at 600 nm, the TN hydrogel shows a similar NIR-responsive temperature, but much higher optical transmittance (∼53%). Besides, of the three hydrogels with similar transmittance, the TN hydrogel shows a much higher NIR-responsive temperature. The TN hydrogel with a low loading of 2D-MoO2 (1.5 mg mL-1) can produce a significant temperature increase of ∼30 °C after the application of 0.8 W cm-2 NIR light irradiation for 15 s. Impressively, the TN hydrogel exhibits excellent anti-fatigue property, keeping a fast response and temperature rise behavior even after 50 times of heating-cooling cycles. The flexibly controllable and reversible deformation is realized by a well-designed bilayer structure even in harsh environments. The transparent and asymmetric bilayer hydrogel is further used as a soft manipulator to capture objects visually and accurately. The NIR light-controlled microvalve based on this composite hydrogel is also demonstrated. This work provides a novel kind of transparent hybrid NIR response hydrogel for the further development of smart, programmable, reversible hydrogel-based actuators and soft robotics.

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.