Screening the phytotoxicity of micro/nanoplastics through non-targeted metallomics with synchrotron radiation X-ray fluorescence and deep learning: Taking micro/nano polyethylene terephthalate as an example.

Microplastics (MPs) and nanoplastics (NPs) are global pollutants with emerging concerns. Methods to predict and screen their toxicity are crucial. Elemental dyshomeostasis can be used to assess toxicity of environmental pollutants. Non-targeted metallomics, combining synchrotron radiation X-ray fluorescence (SRXRF) and machine learning, has successfully differentiated cancer patients from healthy individuals. The whole idea of this work is to screen the phytotoxicity of nano polyethylene terephthalate (nPET) and micro polyethylene terephthalate (mPET) through non-targeted metallomics with SRXRF and deep learning algorithms. Firstly, Seed germination, seedling growth, photosynthetic changes, and antioxidant activity were used to evaluate the toxicity of mPET and nPET. It was showed that nPET, at 10 mg/L, was more toxic to rice seedlings, inhibiting growth and impairing chlorophyll content, MDA content, and SOD activity compared to mPET. Then, rice seedling leaves exposed to nPET or mPET was examined with SRXRF, and the SRXRF data was differentiated with deep learning algorithms. It was showed that the one-dimensional convolutional neural network (1D-CNN) model achieved 98.99% accuracy without data preprocessing in screening mPET and nPET exposure. In all, non-targeted metallomics with SRXRF and 1D-CNN can effectively screen the exposure and phytotoxicity of nPET/mPET and potentially other emerging pollutants. Further research is needed to assess the phytotoxicity of different types of MPs/NPs using non-targeted metallomics.

Chitosan-coated hydroxyapatite and drug-loaded polytrimethylene carbonate/polylactic acid scaffold for enhancing bone regeneration.

Biocompatible polymers and drug-delivery scaffolds have driven development in bone regeneration. In this study, we fabricated a chitosan (CS)-coated polytrimethylene carbonate (PTMC)/polylactic acid (PLLA)/oleic acid-modified hydroxyapatite (OA-HA)/vancomycin hydrochloride (VH) microsphere scaffold for drug release with excellent biocompatibility. The incorporation of PLLA, OA-HA, and VH into PTMC microspheres not only slowed the biodegradability of the scaffold but also enhanced its mechanical properties and surface properties. Moreover, the CS coating stimulated extensive adhesion of osteoblasts before OA-HA incorporation, which facilitated the controlled release of OA-HA. The scaffolds were characterized via scanning electron microscopy, in vitro comprehensive performance testing, cell culturing, and microcomputer tomography scanning. The results indicated that the surface of the composite microsphere scaffold was suitable for osteoblast adhesion. Additionally, the release of OA-HA stimulated osteogenic proliferation. Our findings suggest that the CS-PTMC/PLLA/OA-HA/VH microsphere scaffold is promising for bone tissue engineering applications.

Biocompatible and biodegradable scaffold based on polytrimethylene carbonate-tricalcium phosphate microspheres for tissue engineering.

Biocompatible polymers and drug delivery vehicles have been driving development in bone regeneration. However, most bone scaffolds show poor degradation and proliferation. In this study, a composite microsphere scaffold was prepared using vancomycin hydrochloride(VH)-loaded polytrimethylene carbonate(PTMC) microsphere (PTMC-VH). Adopting a thermal technique, a three-dimensional oleic acid-modified tricalcium phosphate (PTMC-OA-TCP)/PTMC-VH microsphere scaffold was prepared. It had a porosity of 41-47 % and pore size of 129-154 µm. The highest drug loading and release efficiency were obtained with the scaffold produced using 2.4 % polymer concentration and 0.5 %polyvinyl alcohol. The scaffold with PTMC-VH microsphereshad enhancedmechanical properties, water absorption capacity, and degradation. In addition, the PTMC-OA-TCP scaffold had comparable performance with bone cement control in terms of bone regeneration in vivo. In summary, the prepared bioactive scaffolds, which had favorable mechanical properties and facilitated osteogenesis, could be a promising alternative for bone cement in bone tissue engineering.

[A comparative study of early degradation of PLLA and PLGA rods at various sites in rabbit].

This study was designed to assess the effect of implantation site and environment on early in vivo degradation behaviors of poly(L-lactide) (PLLA) and poly(L-lactide-co-glycolide) (PLGA) copolymer. The rods were implanted at two sites in each of 24 New Zealand White rabbits. The first site was within the suprapatellar bursa of the joint cavities (JC) and the second site was in the opposite condyles of femurs (CF). Three rabbits of each group underwent explantation of rods after 4, 8, 12, and 16 weeks. At each interval, measures were taken to evaluate the molecular weight, shear strength, weight loss and thermal properties of PLLA and PLGA. It was found that PLGA degraded slightly faster than PLLA. After 16 weeks, PLLA's initial inherent viscosity of 4.6 decreased to about 3.4 in both implantation sites while that of PLGA decreased from 4.6 to about 2.2. Both PLGA and PLLA showed enough shear strength retention in 16 weeks (> or = 53MPa) within 16 weeks. Autocatalysis mechanism was confirmed by the fact of accelerated weight loss of PLGA after 8 weeks and of PLLA after 12 weeks. The results revealed that PLGA could be a promising candidate material as a replacement of PLLA in internal fixation of bone fractures, and no significant difference of early in vivo degradation behaviors between PLLA and PLGA was observed in regard to different implantation sites in 16 weeks.

In vitro and in vivo degradation of potential anti-adhesion materials: Electrospun membranes of poly(ester-amide) based on l-phenylalanine and p-(dioxanone).

Electrospun membranes of poly(p-dioxanone-co-l-phenylalanine) (PDPA) hold potential as an anti-adhesion material. Since adjustable degradation properties are important for anti-adhesion materials, in this study, the in vitro and in vivo degradation processes of PDPA electrospun membranes were investigated in detail. The morphological analysis of these membranes revealed the main degradation conditions of PDPA membranes. The weight remaining and molecular weight variation showed that the overall degradation rate of the membranes could be adjusted by modulating the molecular structure of the PDPAs. Especially, α-chymotrypsin could catalyze the degradation process of PDPAs. Based on these results, the in vitro degradation mechanism was demonstrated, and confirmed by 1 H NMR of the hydrolysis products. Finally, the in vivo degradation and biocompatibility of different PDPAs were investigated. The kinetic study showed that the in vitro and in vivo molecular weight loss of PDPAs have the first-order characteristics. The in vivo degradation rate of the most Phe-containing PDPA-3 is the slowest, and this result relates to the biocompatibilities of PDPAs. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1369-1378, 2017.

Mechanism of inhibition on L929 rat fibroblasts proliferation induced by potential adhesion barrier material poly(p-dioxanone-co-L-phenylalanine) electrospun membranes.

Fibroblast plays an important role in the occurrence of postoperative tissue adhesion; materials that have particular "cell-material" interactions to inhibit proliferation of fibroblast will be excellent potential adhesion barriers. In the current study, we synthesized copolymers of p-dioxanone and L-phenylalanine (PDPA) and evaluated the mechanism of its particular inhibition effect on L929 fibroblast proliferation when used as a culture surface. PDPA electrospun membranes could induce apoptosis of L929 fibroblasts. We hypothesized there were two reasons for the apoptosis induction: one was the ability to facilitate cell adhesion of materials, and the other was production of the degradation product, L-phenylalanine. Ninhydrin colorimetric results revealed that L-phenylalanine was continuously released during the culture process and could induce apoptosis in L929 cells. Relatively poor cell adhesion and constant release of L-phenylalanine made PDPA-1 to be the most efficient polymer for the induction of apoptosis. Analysis of apoptosis-related genes revealed that PDPA-induced apoptosis might be performed in a mitochondrial-dependent pathway. But poly(p-dioxanone)-induced apoptosis might occur in a c-Myc independent pathway that was different from PDPA.

Facile synthesis of poly(3,4-ethylenedioxythiophene) film via solid-state polymerization as high-performance Pt-free counter electrodes for plastic dye-sensitized solar cells.

A high-performance Pt-free counter electrode (CE) based on poly(3,4-ethylenedioxythiophene) (PEDOT) film for plastic dye-sensitized solar cells (DSCs) has been developed via a facile solid-state polymerization (SSP) approach. The polymerization was simply initiated by sintering the monomer, 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT), at the temperature of 80 °C, which can be applied on the plastic substrate. The cyclic voltammetry measurements revealed that the catalytic activity of the SSP-PEDOT CE for triiodide reduction is comparable with that of the Pt CE. Under optimized conditions, the power conversion efficiency of a DSC with a N719-sensitized TiO2 photoanode and the SSP-PEDOT CE is 7.04% measured under standard 1 sun illumination (100 mW cm(-2), AM 1.5), which is very close to that of the device fabricated under the same conditions with a conventional thermally deposited Pt CE (7.35%). Furthermore, taking advantage of the compatibility of the SSP-PEDOT with the plastic substrates, a full plastic N719-sensitized TiO2 solar cell was demonstrated, and an efficiency of 4.65% was achieved, which is comparable with the performance of a plastic DSC with a sputter-deposited Pt CE (5.38%). These results demonstrated that solid-state polymerization initiated at low temperature is a facile and low-cost method of fabricating the high-performance Pt-free CEs for plastic DSCs.

Poly(para-dioxanone)/inorganic particle composites as a novel biomaterial.

In this work, poly(para-dioxanone) (PPDO) was mixed with 1% (by weight) calcium carbonate (CaCO(3)), beta-tricalcium phosphate (beta-TCP), or calcium sulphate dihydrate (CSD) by solution co-precipitation. Samples were compression molded into bars using a platen-vulcanizing press. The morphology, thermal and mechanical properties, and crystalline structure of the composites were investigated using differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and X-ray diffraction. All results suggest that three types of inorganic particle in this system promote the crystallinity of PPDO and act as an effective nucleating agent: the relative degree of crystallinity of PPDO increased from 30.74% to 100%, and the crystallization temperature of PPDO was increased by 18 degrees C. On the other hand, the mechanical properties of PPDO were changed by the presence of inorganic particles: the tensile strength of PPDO/CSD increased by 11.46%.