Biodegradable Polymersomes with Structure Inherent Fluorescence and Targeting Capacity for Enhanced Photo-Dynamic Therapy.

Biodegradable nanostructures displaying aggregation-induced emission (AIE) are desirable from a biomedical point of view, due to the advantageous features of loading capacity, emission brightness, and fluorescence stability. Herein, biodegradable polymers comprising poly (ethylene glycol)-block-poly(caprolactone-gradient-trimethylene carbonate) (PEG-P(CLgTMC)), with tetraphenylethylene pyridinium-TMC (PAIE) side chains have been developed, which self-assembled into well-defined polymersomes. The resultant AIEgenic polymersomes are intrinsically fluorescent delivery vehicles. The presence of the pyridinium moiety endows the polymersomes with mitochondrial targeting ability, which improves the efficiency of co-encapsulated photosensitizers and improves therapeutic index against cancer cells both in vitro and in vivo. This contribution showcases the ability to engineer AIEgenic polymersomes with structure inherent fluorescence and targeting capacity for enhanced photodynamic therapy.

Antibacterial functionalization of cotton and cotton/polyester fabrics applying hybrid coating of copper/chitosan nanocomposites loaded polymer blends via gamma irradiation.

In the present work, copper/chitosan nanocomposites (Cu/CS) were prepared in an aqueous solution in the presence of CS as stabilizer and CuSO4·5H2O precursor. The Cu/CS NPs formation was proved through transmission electron microscopy (TEM), Dynamic light scattering (DLS), Fourier Transform infrared (FT-IR) spectroscopy and XRD diffraction. Cotton and cotton/polyester fabrics were gamma-radiation grafted by padding to pickup of 100%, in nanocomposites based on Cu/CS NPs loaded in polymer blends of poly(vinyl alcohol) (PVA) and plasticized starch (PLST). The grafted fabrics were characterized in terms of tensile mechanical, crease recovery and water absorption properties. The results showed that cotton fabrics displayed higher water absorption (%) than cotton/polyester fabrics for all PVA/PLST compositions and water absorption was found to decrease with increasing the ratio of PVA in the PVA/PLST blends. Cotton/polyester fabrics displays crease recovery angle (CRA) value of 147.6 upon treated with PVA/PLST (80/20%) and gamma irradiated to 30 kGy compared to CRA value of 125.0 for cotton fabrics treated under the same conditions. For cotton fabrics, the tensile strength was largely depends on the irradiation dose, in which the tensile strength of the treated fabric with the different formulations is higher than the untreated fabric. The antimicrobial activity of the fabrics against gram-positive bacteria (Staphylococcus aurous) and gram-negative bacteria (Escherichia coli) was investigated. In case of gram-positive bacteria cotton fabric showed the highest impact, for both 50/50 and 20/80 PVA/PLST of 14 and 14.5 mm inhibition zone, whilst, cotton/polyester fabric recorded 6 and 5 mm inhibition zone against gram-negative bacteria for 50/50 and 20/80 PVA/PLST, respectively.

Surface Modification of PLLA, PTFE and PVDF with Extreme Ultraviolet (EUV) to Enhance Cell Adhesion.

Recently, extreme ultraviolet (EUV) radiation has been increasingly used to modify polymers. Properties such as the extremely short absorption lengths in polymers and the very strong interaction of EUV photons with materials may play a key role in achieving new biomaterials. The purpose of the study was to examine the impact of EUV radiation on cell adhesion to the surface of modified polymers that are widely used in medicine: poly(tetrafluoroethylene) (PTFE), poly (vinylidene fluoride) (PVDF), and poly-L-(lactic acid) (PLLA). After EUV surface modification, which has been performed using a home-made laboratory system, changes in surface wettability, morphology, chemical composition and cell adhesion polymers were analyzed. For each of the three polymers, the EUV radiation differently effects the process of endothelial cell adhesion, dependent of the parameters applied in the modification process. In the case of PVDF and PTFE, higher cell number and cellular coverage were obtained after EUV radiation with oxygen. In the case of PLLA, better results were obtained for EUV modification with nitrogen. For all three polymers tested, significant improvements in endothelial cell adhesion after EUV modification have been demonstrated.

In situ preparation of gold-polyester nanoparticles for biomedical imaging.

The synthesis and application of gold nanoparticles (AuNPs) have attracted much attention due to their interesting optical and chemical properties, as well as their utility in imaging, therapeutics, sensors, electronics, and catalysis. AuNPs are synthesized using multiple approaches, followed by chemical modification or encapsulation, to enhance their colloidal stability, biocompatibility, and targeting. Here, we report the one-step synthesis of gold-polyester nanoparticles for use as an imaging agent. The AuNPs were prepared inside polymeric NPs by means of ultraviolet irradiation of a gold salt in the presence of Irgacure I-2959 photoinitiator. We monitored the kinetic growth and nucleation of AuNPs (in vitro and ex vivo) over time using spectral analysis. Moreover, we investigated the cytotoxicity, localized plasmonic surface resonance (LSPR), and cellular imaging capabilities of the Au-polyester nanoparticles. The resulting Au-polyester NPs were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), dynamic light scattering (DLS), and transmission electron microscopy (TEM) to probe their chemical structure, size, zeta potential (ζ), and morphology, respectively. Furthermore, in vitro experiments showed that the NP formulation is stable over time and exhibits negligible toxicity against 3T3 fibroblast and U-87 MG glioblastoma cells. The results also demonstrated that the Au-polyester NPs exhibit excellent cellular imaging properties. This one-step strategy goes beyond current syntheses of gold-polyester nanoparticles because it can be used to synthesize the imaging agent in situ (i.e., in living cells) in lieu of conventional ex situ approaches.

Photo-crosslinked anhydride-modified polyester and -ethers for pH-sensitive drug release.

Photo-crosslinkable polymers have a great potential for the delivery of sensitive drugs. They allow preparation of drug releasing devices by photo-crosslinking, thus avoiding high processing temperatures. In this study, the hydrolysis behavior and drug release of three different photo-crosslinkable poly(ether anhydride)s and one poly(ester anhydride) were investigated. Three-arm poly(ethylene glycol) or polycaprolactone was reacted with succinic anhydride to obtain carboxylated macromers, and further functionalized with methacrylic anhydride to form methacrylated marcromers with anhydride linkages. The synthetized macromers were used to prepare photo-crosslinked matrices with different hydrolytic degradation times for active agent release purposes. The hydrolysis was clearly pH-sensitive: polymer networks degraded slowly in acidic conditions, and degradation rate increased as the pH shifted towards basic conditions. Drug release was studied with two water-soluble model drugs lidocaine (234 mol/g) and vitamin B12 (1355 g/mol). Vitamin B12 was released mainly due to polymer network degradation, whereas smaller molecule lidocaine was released also through diffusion and swelling of polymer network. Only a small amount of vitamin B12 was released in acidic conditions (pH 1.3 and pH 2.1). These polymers have potential in colon targeted drug delivery as the polymer could protect sensitive drugs from acidic conditions in the stomach, and the drug would be released as the conditions change closer to neutral pH in the intestine.

Impact of sterilization by electron beam, gamma radiation and X-rays on electrospun poly-(ε-caprolactone) fiber mats.

Biodegradable polymers such as polycaprolactone (PCL) are increasingly used for electrospinning substrates for tissue engineering. These materials offer great advantages such as biocompatibility and good mechanical properties. However, in order to be approved for human implantation they have to be sterilized. The impact of commonly used irradiation sterilization methods on electrospun PCL fiber mats was investigated systematically. Electron beam (ß-irradiation), gamma and X-ray irradiation with two different doses (25 and 33 kGy) were investigated. To determine the impact on the fiber mats, mechanical, chemical, thermal properties and crystallinity were investigated. Irradiation resulted in a significant decrease in molecular weight. At the same time, crystallinity of fiber mats increased significantly. However, the mechanical properties did not change significantly upon irradiation, mostly likely because effects of a lower molecular weight were balanced with the higher degree of crystallinity. The irradiation effects were dose dependent, a higher irradiation dose led to stronger changes. Gamma irradiation seemed to be the least suited method, while electron beams (ß irradiation) had a lower impact. Therefore, ß irradiation is recommended as sterilization method for electrospun PCL fiber mats.

Radiochromic film containing poly(hexa-2,4-diynylene adipate) as a radiation dosimeter.

A radiation-sensitive polymer poly(hexa-2,4-diynylene adipate) (PHDA) was synthesized and incorporated into polyvinyl butyral films for radiation dose measurements in the 0.5 - 60 kGy range. PHDA undergoes crosslinking polymerization upon exposure to γ-rays, which changes its color from very pale yellow to deep orange-yellow. The color change is directly related to the absorbed dose. The absorption spectrum of the irradiated films features one absorption band around 500 nm with a shoulder around 465 nm. With increasing absorbed dose, the two bands grow in intensity and move towards higher wavelengths. The dosimeter is nearly insensitive to variations of the humidity in the range of 0-54% and temperature in the range of 30-45 °C during irradiation. The color intensifies after irradiation, both in the dark and in the light at room temperature, which reflects the continuing crosslinking polymerization. However, at - 4 °C, the color intensity does not change with time.

Titania nanowires functionalized polyester fabrics with enhanced photocatalytic and antibacterial performances.

Flexible organic fabrics coated with titania find wide applications in pollutant degradations and antibiosis. Because of the enhanced charge separations, TiO2 with one-dimensional nanostructures exhibits photocatalytic activity superior to that of nanoparticulate films; however, only the later has been achieved on organic substrates through commonly sol-gel techniques till now. In this study, radially aligned TiO2 nanowires were precipitated on polyester fabrics through multi-steps of surface roughening, sol-gel TiO2 seeding, hydrogen titanate nanobelts precipitation, and finally sulfuric acid treatment. Both mesoporous anatase TiO2 nanowires and single-crystalline rutile TiO2 nanorods have been achieved, which, together with some unchanged titanate nanobelts, exhibited an overall narrowed band gap of ca. 2.50eV. The TiO2 nanowires on flexible PET fabrics showed higher photocatalytic activity towards degradations of not only rhodamine B in water but also toluene gas in air under UV light illumination, when compared with either TiO2 nanotube array or commercial Degussa P25 nanoparticulate films on metallic Ti substrates. Remarkable sterilization of E. coli and S. epidermidis under visible light irradiation was also achieved. The excellent photocatalytic and antibacterial performances were attributed to the unique mixed 1D nanostructures, phase junctions, abundant surface hydroxyl groups, and the narrowed band gap.

Preparation of core-crosslinked linear-dendritic copolymer micelles with enhanced stability and their application for drug solubilisation.

In this study we explore the preparation of core-crosslinked micelles of linear-dendritic methoxy-poly(ethylene glycol) (MPEG)-co-poly(ester-sulfide) (PES) polymers to improve the stability of such polymeric micelle systems against premature disintegration and drug release. A series of MPEG-PES copolymers were synthesised via stepwise reactions of acetylation and thiol-ene photoreaction. Surface tension measurement showed that the copolymers with ethenyl surface groups could self-associate in dilute aqueous solutions to form micelles. Crosslinking within the micelle cores in the presence of dithioerythritol (DTT) linker was initiated under UV radiation. The formation of core-crosslinked micelles was confirmed by HPLC in combination with charged aerosol detection (CAD). The copolymers were found to readily hydrolyse under acidic conditions due to the ester-containing dendrons. Drug solubilisation capacities of the micellar solutions were determined using griseofulvin as a poorly water-soluble model drug. The solubility of griseofulvin showed a 10-fold enhancement in 1% w/v micelle solution and increased with the concentration of the copolymers. Drug release studies indicated that a more sustained release of griseofulvin was achieved for the core-crosslinked micelles compared to the non-crosslinked micelles, attributable to greater stability of the crosslinked core structure. The findings of this study present a new pathway towards developing biodegradable polymeric nanocarriers.

Evaluation of the migration of chemicals from baby bottles under standardised and duration testing conditions.

After the prohibition of bisphenol-A-containing polycarbonate baby bottles in the European Union (EU), alternative materials, such as polypropylene, polyethersulphone, Tritan™ copolyester, etc., have appeared on the market. Based on an initial screening and in vitro toxicity assessment, the most toxic migrating compounds were selected to be monitored and quantified using validated GC- and LC-QqQ-MS methods. The effect of several 'real-life-use conditions', such as microwave, sterilisation and dishwasher, on the migration of different contaminants was evaluated by means of duration tests. These results were compared with a reference treatment (filling five times with pre-heated simulant at 40°C) and with the legal EU 'repetitive-use conditions' (three migrations, 2 h at 70°C). Analysis of the third migration step of the EU repetitive-use conditions (which has to comply with the EU legislative migration limits) showed that several non-authorised compounds were observed in some baby bottles exceeding 10 µg kg(-1). However, all authorised compounds were detected well below their respective specific migration limits (SMLs). The reference experiment confirmed the migration of some of the compounds previously detected in the EU repetitive-use experiment, though at lower concentrations. Analysis of extracts from the microwave and dishwasher experiments showed a reduction in the migration during the duration tests. In general, the concentrations found were low and comparable with the reference experiment. Similar observations were made for the two sterilisation types: steam and cooking sterilisation. However, steam sterilisation seems to be more recommended for daily use of baby bottles, since it resulted in a lower release of substances afterwards. Repeated use of baby bottles under 'real-life' conditions showed no increase in the migration of investigated compounds and, after some time, the migration of these compounds even became negligible.

Evaluation of photodynamic activity, photostability and in vitro drug release of zinc phthalocyanine-loaded nanocapsules.

Nanocapsule formulations containing zinc phthalocyanine (ZnPc) were investigated as drug delivery systems for use in photodynamic therapy (PDT). ZnPc loaded chitosan, PCL, and PCL coated with chitosan nanocapsules were prepared and characterized by means of their physicochemical properties, photodynamic activity, photostability and drug release profile. All formulations presented nanometric hydrodynamic radius, around 100 nm, low polydispersity index (0.08-0.24), slightly negative zeta potential for PCL nanoparticles and positive zeta potential for suspension containing chitosan. Encapsulation efficiencies were higher than 99%. The capacity of ZnPc loaded nanocapsules to produce cytotoxic singlet oxygen ((1)O2) by irradiation with red laser was monitored using 1.3-diphenylisobenzofuran as a probe. The singlet oxygen quantum yields (ΦΔ) for ZnPc loaded chitosan nanocapsules were high and similar to that of the standard (ZnPc in DMSO), displaying excellent ability to generate (1)O2. The photosensitizer loaded nanocapsules are photostable in the timescale usually utilized in PDT and only a small photobleaching event was observed when a light dose of 610J/cm(2) was applied. The in vitro drug release studies of ZnPc from all nanocapsules demonstrated a sustained release profile controlled by diffusion, without burst effect. The nature of the polymer and the core type of the nanocapsules regulated ZnPc release. Thus, the nanocapsules developed in this work are a promising strategy to be employed in PDT.

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization.

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate.

Local ultraviolet laser irradiation for gradients on biocompatible polymer surfaces.

Generation of supporting structures, which guide cell growth, is a challenging task in the field of tissue engineering. Cell guidance properties of a scaffold are important in the field of neuronal regeneration. Those guiding structures can provide guidance just by mechanical stimulus or by chemical stimuli like cell signaling molecules. For an enhanced guidance, chemical gradients are under investigation. With this study, we show that ultraviolet laser irradiation is a useful tool to activate polymer surfaces with a high temporal and spatial resolution. We demonstrated that poly(methyl methacrylate) (PMMA) and poly-ε-caprolactone (PCL) can be locally activated and functionalized with amine groups that can be used for immobilization of arginine-glycine-aspartic acid (RGD) peptide. The immobilized RGD was detected by neuronal B35 cells. By defined pulse accumulation functionalization density on the surface can be varied for the generation of gradients. We demonstrated that PMMA and PCL have different process windows for functionalization. Although PMMA has a very small process window for activation, PCL allows the generation of stepwise functionalization. The presented technology can help to develop assays for the analysis of cell migration and neuronal regeneration due to flexible patterning easily realized by changing the irradiation parameters.

Challenges in the characterization of plasma-processed three-dimensional polymeric scaffolds for biomedical applications.

Low-temperature plasmas offer a versatile method for delivering tailored functionality to a range of materials. Despite the vast array of choices offered by plasma processing techniques, there remain a significant number of hurdles that must be overcome to allow this methodology to realize its full potential in the area of biocompatible materials. Challenges include issues associated with analytical characterization, material structure, plasma processing, and uniform composition following treatment. Specific examples and solutions are presented utilizing results from analyses of three-dimensional (3D) poly(ε-caprolactone) scaffolds treated with different plasma surface modification strategies that illustrate these challenges well. Notably, many of these strategies result in 3D scaffolds that are extremely hydrophilic and that enhance human Saos-2 osteoblast cell growth and proliferation, which are promising results for applications including tissue engineering and advanced biomedical devices.

Thymine modified amphiphilic biodegradable copolymers for photo-cross-linked micelles as stable drug carriers.

A photo-cross-linked micelle is synthesized via photodimerization of thymine moieties fabricated from amphiphilic block copolymers (mPEG-b-P(LA-co-MPT). The crosslinking behavior is monitored by UV-Vis spectra and (1) H NMR. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) showed that cross-linked micelles had smaller sizes than their uncross-linked precursors. In vitro studies reveal that cross-linking of the micelle cores results in a slow drug release and faster cellular uptake in comparison with uncross-linked ones in MCF-7 and Hela cells. Moreover, the paclitaxel (PTX)-loaded core-cross-linked micelles exhibit similar anticancer efficacy as free PTX. This work provides a convenient tool for designing a more stable structure in the blood circulation to realize a controlled drug delivery.

Poly(ε-caprolactone)-based copolymers bearing pendant cyclic ketals and reactive acrylates for the fabrication of photocrosslinked elastomers.

Block copolymers of poly(ethylene glycol) and poly(ε-caprolactone) (PCL) with chemically addressable functional groups were synthesized and characterized. Ring-opening polymerization of ε-caprolactone (CL) and 1,4,8-trioxaspiro-[4,6]-9-undecanone (TSU) using α-methoxy, ω-hydroxyl poly(ethylene glycol) as the initiator afforded a copolymer with cyclic ketals being randomly distributed in the hydrophobic PCL block. At an initiator/catalyst molar ratio of 10/1 and a TSU/CL weight ratio of 1/4, a ketal-carrying copolymer (ECT2-CK) with Mn of 52 kDa and a ketal content of 15 mol.% was obtained. Quantitative side-chain deacetalization revealed the reactive ketones without noticeable polymer degradation. In our study, 10 mol.% of cyclic ketals were deprotected and the ketone-containing copolymer was designated as ECT2-CO. Reaction of ECT2-CO with 2-(2-(aminooxy)acetoxy)-ethyl acrylate gave rise to an acrylated product (ECT2-AC) containing an estimated 3-5 acrylate groups per chain. UV-initiated radical polymerization of ECT2-AC in dichloromethane resulted in a crosslinked network (xECT2-AC). Thermal and morphological analyses employing differential scanning calorimetry and atomic force microscopy operated in PeakForce Tapping mode revealed the semicrystalline nature of the network, which contained stiff crystalline lamellae dispersed in a softer amorphous interstitial. Macroscopic and nanoscale mechanical characterizations showed that ECT2-CK exhibited a significantly lower modulus than PCL of a similar molecular weight. Whereas ECT2-CK undergoes a plastic deformation with a distinct yield point and a cold-drawing region, xECT2-AC exhibits a compliant, elastomeric deformation with a Young's modulus of 0.5±0.1 MPa at 37°C. When properly processed, the crosslinked network exhibited shape-memory behaviors, with shape fixity and shape recovery values close to 1 and a shape recovery time of less than 4s at 37°C. In vitro studies showed that xECT2-AC films did not induce any cytotoxic effects on the cultured mesenchymal stem cells. The crosslinkable polyester copolymers can be potentially used as tissue engineering scaffolds and minimally invasive medical devices.

Determination of the interfacial rheological properties of a poly(DL-lactic acid)-encapsulated contrast agent using in vitro attenuation and scattering.

The stabilizing encapsulation of a microbubble-based ultrasound contrast agent (UCA) critically affects its acoustic properties. Polymers, which behave differently from materials commonly used (i.e., lipids or proteins) for monolayer encapsulation, have the potential for better stability and improved control of encapsulation properties. Air-filled microbubbles coated with poly(DL-lactic acid) (PLA) are characterized here using in vitro acoustic experiments and several models of encapsulation. The interfacial rheological properties of the encapsulation are determined according to each model using attenuation of ultrasound through a suspension of microbubbles. Then the model predictions are compared with scattered non-linear (sub- and second harmonic) responses. For this microbubble population (average diameter, 1.9 µm), the peak in attenuation measurement indicates a weighted-average resonance frequency of 2.5-3 MHz, which, in contrast to other encapsulated microbubbles, is lower than the resonance frequency of a free bubble of similar size (diameter, 1.9 µm). This apparently contradictory result stems from the extremely low surface dilational elasticity (around 0.01-0.07 N/m) and the reduced surface tension of the poly(DL-lactic acid) encapsulation, as well as the polydispersity of the bubble population. All models considered here are shown to behave similarly even in the non-linear regime because of the low surface dilational elasticity value. Pressure-dependent scattering measurements at two different excitation frequencies (2.25 and 3 MHz) revealed strongly non-linear behavior with 25-30 dB and 5-20 dB enhancements in fundamental and second-harmonic responses, respectively, for a contrast agent concentration of 1.33 µg/mL in the suspension. Sub-harmonic responses are registered above a relatively low generation threshold of 100-150 kPa, with up to 20 dB enhancement beyond that pressure. Numerical predictions from all models show good agreement with the experimentally measured fundamental response, but not with the experimental second-harmonic response. The characteristic features of sub-harmonic responses and the steady response beyond the threshold are matched well by model predictions. However, prediction of the threshold value depends on estimated properties and size distribution. The variation in size distribution from sample to sample leads to variation in estimates of encapsulation properties: the lowest estimated value for surface dilational viscosity better predicts the sub-harmonic threshold.

Photocrosslinkable biodegradable elastomers based on cinnamate-functionalized polyesters.

Synthetic biodegradable elastomers are an emerging class of materials that play a critical role in supporting innovations in bioabsorbable medical implants. This paper describes the synthesis and characterization of poly(glycerol-co-sebacate)-cinnamate (PGS-CinA), a biodegradable elastomer based on hyperbranched polyesters derivatized with pendant cinnamate groups. PGS-CinA can be prepared via photodimerization in the absence of photoinitiators using monomers that are found in common foods. The resulting network exhibits a Young's modulus of 50.5-152.1kPa and a projected in vitro degradation half-life time between 90 and 140days. PGS-CinA elastomers are intrinsically cell-adherent and support rapid proliferation of fibroblasts. Spreading and proliferation of fibroblasts are loosely governed by the substrate stiffness within the range of Young's moduli in PGS-CinA networks that were prepared. The thermo-mechanical properties, biodegradability and intrinsic support of cell attachment and proliferation suggest that PGS-CinA networks are broadly applicable for use in next generation bioabsorable materials including temporary medical devices and scaffolds for soft tissue engineering.

Electrospinning and crosslinking of low-molecular-weight poly(trimethylene carbonate-co-(L)-lactide) as an elastomeric scaffold for vascular engineering.

The growth of suitable tissue to replace natural blood vessels requires a degradable scaffold material that is processable into porous structures with appropriate mechanical and cell growth properties. This study investigates the fabrication of degradable, crosslinkable prepolymers of l-lactide-co-trimethylene carbonate into porous scaffolds by electrospinning. After crosslinking by γ-radiation, dimensionally stable scaffolds were obtained with up to 56% trimethylene carbonate incorporation. The fibrous mats showed Young's moduli closely matching human arteries (0.4-0.8MPa). Repeated cyclic extension yielded negligible change in mechanical properties, demonstrating the potential for use under dynamic physiological conditions. The scaffolds remained elastic and resilient at 30% strain after 84days of degradation in phosphate buffer, while the modulus and ultimate stress and strain progressively decreased. The electrospun mats are mechanically superior to solid films of the same materials. In vitro, human mesenchymal stem cells adhered to and readily proliferated on the three-dimensional fiber network, demonstrating that these polymers may find use in growing artificial blood vessels in vivo.

Photodegradable polyesters for triggered release.

Photodegradable polyesters were synthesized with a photolabile monomer 2-nitrophenylethylene glycol and dioyl chlorides with different lengths. These polymers can be assembled to form polymeric particles with encapsulation of target substances. Light activation can degrade these particles and release payloads in both aqueous solutions and RAW 264.7 cells.