This paper explores whether the photochromic reaction of a molecule embedded in a polymer film can affect its surface adhesion properties, as measured by shear strength and delamination in water. The adherence of polystyrene (PS) to glass was chosen as a model system. Two commercially available photochromesa spiropyran derivative 1′,3′-dihydro-1′,3′,3′-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2′-(2H)-indole]) (SP) and a diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5hexafluoro-1-cyclopentene (DAE)are studied in detail. Both photochromic reactions can significantly enhance the adhesion of PS to a glass surface. The most dramatic results were obtained for PS/SP films, whose shear strength increased by a factor of 7 while the delamination rate was suppressed by at least 2 orders of magnitude after exposure to UV light. The enhanced polymer adhesion could only be partially reversed, even after extended exposure to visible light completely regenerated the UV-absorbing isomer. Nanoindentation and heating experiments suggest that the limited reversibility results from changes in polymer internal structure. We hypothesize that the adhesion changes arise from localized polymer and molecular motions that eliminate void spaces and surface gaps at the polymer−glass interface. The results show that adhesive forces between a prototypical polymer and an inorganic substrate can be modulated by photochromic reactions of embedded molecules.

Photoisomerization of molecules dissolved in a polymer film can modulate its properties. In a previous paper (Mostafavi, S. H.;et al. Macromolecules 2018et al. Macromolecules , 51, 2388et al. Macromolecules −2394, it was found that the ultraviolet light-induced photoisomerization of spiropyran dopants could substantially increase adhesion to a glass surface. In this work, a different photochromic reaction, the visible-light-induced cyclization of a donor−acceptor Stenhouse adduct (DASA), leads to the opposite effect: the deadhesion of a polystyrene film from a clean glass surface. Measurements of the shear and pull-off adhesion strengths before and after visible irradiation show a light-induced decrease of 20−30%. The time required for delamination in water shows an even more dramatic decrease of 90%. Changes in the water contact angle and other measurements suggest that molecular-level noncovalent interactions between the polymer and glass are weakened after photoisomerization, possibly due to the molecular contraction of the DASA that disrupts the interaction between its amine groups and the surface silanols. The ability to reduce polymer adhesion using visible light enables the controlled release of dye molecules from a glass container, where these have been stored as a dry powder, into an aqueous solution. Embedding photochromic molecules in a polymer can lead to new effects that may have practical applications in stimuli-responsive materials.

BackgroundNanoparticles (NPs) play an important role in anticancer delivery systems. Surface modified NPs with hydrophilic polymers such as human serum albumin (HSA) have long half-life in the blood circulation system.MethodsThe method of modified nanoprecipitation was utilized for encapsulation of paclitaxel (PTX) in poly (lactic-co-glycolic acid) (PLGA). Para-maleimide benzoic hydrazide was conjugated to PLGA for the surface modifications of PLGA NPs, and then HSA was attached on the surface of prepared NPs by maleimide attachment to thiol groups (cysteines) of albumin. The application of HSA provides for the longer blood circulation of stealth NPs due to their escape from reticuloendothelial system (RES). Then the physicochemical properties of NPs like surface morphology, size, zeta potential, and in-vitro drug release were analyzed.ResultsThe particle size of NPs ranged from 170 to 190 nm and increased about 20–30 nm after HSA conjugation. The zeta potential was about -6 mV and it decreased further after HSA conjugation. The HSA conjugation in prepared NPs was proved by Fourier transform infrared (FT-IR) spectroscopy, faster degradation of HSA in Differential scanning calorimetry (DSC) characterization, and other evidences such as the increasing in size and the decreasing in zeta potential. The PTX released in a biphasic mode for all colloidal suspensions. A sustained release profile for approximately 33 days was detected after a burst effect of the loaded drug. The in vitro cytotoxicity evaluation also indicated that the HSA NPs are more cytotoxic than plain NPs.ConclusionsHSA decoration of PLGA NPs may be a suitable method for longer blood circulation of NPs.

Previous work has shown that photoisomerization of dopant molecules in a polystyrene film can either enhance or suppress its adhesion to a polar glass surface (MostafaviS. H. Mostafavi, S. H. Macromolecules20185123882394; MostafaviS. H. Mostafavi, S. H. Macromolecules20195263116317). In this paper, a different polymer host, Zeonex (ZX), is used in conjunction with the photochrome spiropyran. Nonpolar ZX has a higher glass transition temperature that makes it resistant to nanoscale mechanical deformations, while the spiropyran (SP) → merocyanine (MC) photoisomerization is a reversible reaction with a large polarity change. Ultraviolet light isomerizes SP to the polar MC form, increasing both the shear and pull-off adhesion forces to a clean glass surface by a factor of 5. Visible irradiation switches it back to the nonpolar SP form and returns the film back to its original weak adhesion, in contrast to the previously studied polystyrene films. The ability of visible light to switch off the polymer–glass adhesion is harnessed to make a light-controlled payload release device as well as to accelerate the polymer film delamination rate in water by a factor of 100. The kinetics of the water delamination, as well as the origin of residual adhesion after switching back to the SP form, are investigated. This work demonstrates how light-controlled noncovalent adhesion can be used as a solvent-free method to remove protective coatings or to disassemble structures.

Abstract. In this study, nanosuspension of stable iodine ( 127 I) was prepared by nanoprecipitation process in microfluidic devices. Then, size of particles was optimized using artificial neural networks (ANNs) modeling. The size of prepared particles was evaluated by dynamic light scattering. The response surfaces obtained from ANNs model illustrated the determining effect of input variables (solvent and antisolvent flow rate, surfactant concentration, and solvent temperature) on the output variable (nanoparticle size). Comparing the 3D graphs revealed that solvent and antisolvent flow rate had reverse relation with size of nanoparticles. Also, those graphs indicated that the solvent temperature at low values had an indirect relation with size of stable iodine ( 127 I) nanoparticles, while at the high values, a direct relation was observed. In addition, it was found that the effect of surfactant concentration on particle size in the nanosuspension of stable iodine ( 127 I) was depended on the solvent temperature.

Background and the purpose of the studyThe purpose of this study was to prepare pegylated poly lactide-co-glycolide (PEG-PLGA) nanoparticles (NPs) loaded with roxithromycin (RXN) with appropriate physicochemical properties and antibacterial activity. Roxithromycin, a semi-synthetic derivative of erythromycin, is more stable than erythromycin under acidic conditions and exhibits improved clinical effects.MethodsRXN was loaded in pegylated PLGA NPs in different drug;polymer ratios by solvent evaporation technique and characterized for their size and size distribution, surface charge, surface morphology, drug loading, in vitro drug release profile, and in vitro antibacterial effects on S. aureus, B. subtilis, and S. epidermidis.Results and conclusionNPs were spherical with a relatively mono-dispersed size distribution. The particle size of nanoparticles ranged from 150 to 200 nm. NPs with entrapment efficiency of up to 80.0±6.5% and drug loading of up to 13.0±1.0% were prepared. In vitro release study showed an early burst release of about 50.03±0.99% at 6.5 h and then a slow and steady release of RXN was observed after the burst release. In vitro antibacterial effects determined that the minimal inhibitory concentration (MIC) of RXN loaded PEG-PLGA NPs were 9 times lower on S. aureus, 4.5 times lower on B. subtilis, and 4.5 times lower on S. epidermidis compared to RXN solution. In conclusion it was shown that polymeric NPs enhanced the antibacterial efficacy of RXN substantially.

The aim of the current study was the development of nanosuspension stability in nanoprecipitation using microfluidic devices. Also, it is desirable to understand how the microfluidic preparation parameters influenced the stability of the stable-iodine ( 127 I) nanosuspension. In optimization process through artificial neural networks (ANNs), the relations between input and output variables were investigated for 37 samples obtained by microfluidic nanoprecipitation process. Solvent temperature, antisolvent flow rate, and solvent flow rate were used as input variables, and the sedimentation time and polydispersity index (PDI) were considered as output parameters. Sedimentation time as an indicator of physical stability of nanosuspension was evaluated by observation of a densely packed sediment. Also, size and PDI of different samples were determined by dynamic light scattering. The size of the optimized sample was confirmed by transmission electron microscopy. The result obtained from modeling showed that increasing solvent temperature and antisolvent flow rate led to a decrease in PDI and an increase in the sedimentation time. The antisolvent flow rate was determined as the most important factor that affected the sedimentation time and PDI. Increasing the solvent flow rate was identified as an adverse factor which increased PDI or decreased formulation's sedimentation time. Optimization using ANN showed that microfluidic preparation parameters of nanosuspension as input variables had potential impacts on output parameters.

The aim of this study was to find a model using artificial neural networks (ANNs) to predict PLGA-PMBH nanoparticles (NPs) size in preparation by modified nanoprecipitation. The input variables were polymer content, drug content, power of sonication and ratio of organic/aqueous phase (i.e. acetone/water), while the NPs size of PLGA-PMBH was assumed as the output variable. Forty samples of PLGA-PMBH NPs containing anticancer drug (i.e. paclitaxel) were synthesized by changing the variable factors in the experiments. The data modeling were performed using ANNs. The effects of input variables (namely, polymer content, drug content, power of sonication and ratio of acetone/water) on the output variables were evaluated using the 3D graphs obtained after modeling. Contrasting the 3D graphs from the generated model revealed that the amount of polymer (PLGA-PMBH) and drug content (PTX) have direct relation with the size of polymeric NPs in the process. In addition, it was illustrated that the ratio of acetone/water was the most important factor affecting the particle size of PLGA-PMBH NPs provided by solvent evaporation technique. Also, it was found that increasing the sonication power (up to a certain amount) indirectly affects the polymeric NPs size however it was directly affected in higher values.