Micron-Sized Thiol-Functional Polysilsesquioxane Microspheres with Open and Interconnected Macropores: Preparation, Characterization and Formation Mechanism.

Polysilsesquioxane (PSQ) microspheres have shown promise in many fields, but previous studies about porous PSQ microspheres are scarce. Herein, we fabricated novel micron-sized thiol-functional polysilsesquioxane (TMPSQ) microspheres with open and interconnected macropores by combining inverse suspension polymerization with two-step sol-gel and polymerization-induced phase separation processes, without using phase-separation-promoting additives or sacrificial templates. The chemical composition of the TMPSQ microspheres was confirmed using FTIR and Raman spectroscopy. The morphology of the TMPSQ microspheres was characterized using SEM and TEM. TGA was employed to test the thermal stability of the TMPSQ microspheres. Mercury intrusion porosimetry and nitrogen adsorption-desorption tests were performed to investigate the pore structure of the TMPSQ microspheres. The results showed that the TMPSQ microspheres had open and interconnected macropores with a pore size of 839 nm, and the total porosity and intraparticle porosity reached 70.54% and 43.21%, respectively. The mechanism of porous generation was proposed based on the morphological evolution observed using optical microscopy. The macropores were formed through the following four steps: phase separation (spinodal decomposition), coarsening, gelation, and evaporation of the solvent. The macropores can facilitate the rapid mass transfer between the outer and inner spaces of the TMPSQ microspheres. The TMPSQ microspheres are promising in various fields, such as catalyst supports and adsorbents.

A smartphone readout device for portable and sensitive estimation of Hg2+ via coumarin-modified paper.

The development of cost-effective sensing system for Hg2+ quantitation is highly demanded for environmental monitoring. In this work, we reported an on-site, rapid and portable smartphone-based Hg2+ sensing system integrating coumarin-modified paper as a probe and smartphone readout device as a processing platform. For fluorescent sensing of Hg2+, the modified paper was fabricated by chemically grafting a coumarin-based probe N-((7-hydroxy-coumarin-3-yl)carbamothioyl)acetamide (HCCA) onto paper, and its physicochemical properties and sensing performance were characterized by elemental analysis, FTIR, XPS, SEM, and fluorescence spectral analysis. The modified paper displayed high selectivity and sensitivity for Hg2+, accompanied with a distinct fluorescence color change. For portable detection of the fluorescent sensors, a smartphone readout device was designed, consisting of a removable 3D-printed hardware device and an application. Remarkably, the smartphone readout device in cooperation with the modified paper is highly selective and sensitive to Hg2+ with the limit of detection (LOD) of 0.46 ppb, which avoids the requirement of sophisticated equipment and complex operation. The cost-effective sensing system based on smartphone shows a great potential for monitoring of Hg2+ in environmental water.

Synthesis and application of a novel polyurethane nanoemulsion bearing coumarin derivative as a "turn-on" fluorescence sensor toward Hg2.

A novel polyurethane (PU-co-HCCA) nanoemulsion bearing coumarin derivative (HCCA) was synthesized as a "turn-on" fluorescent probe and used to modify filter paper, and its sensing properties were investigated. Results showed that PU-co-HCCA nanoemulsion exhibited high selectivity and excellent sensitivity toward Hg2+ over other metal ions, and possessed excellent fluorescence quantum yields of 0.976, ppb-levels detection limits of 1.61 ppb and large Stokes shifts of 101 nm. Meanwhile, as an application example of as-prepared PU-co-HCCA nanoemulsion, a Hg2+ test paper was prepared by modifying filter paper with PU-co-HCCA nanoemulsion, and results indicated that the test paper is portable and convenient and has a wide working pH range. We believe that the PU-co-HCCA nanoemulsion and the modified filter paper can provide a new design principle for the application of fluorescence sensors for metal ions including Hg2+.

Preparation and Characterization of a Novel Waterborne Lambda-Cyhalothrin/Alkyd Nanoemulsion.

Inefficient usage and overdosage of conventional pesticide formulations has resulted in large economic losses and environmental pollution due to their poor water solubility and weak adhesion to foliage. In order to develop a green and efficient pesticide formulation, a kind of alkyd resin (AR) based on vegetable oil was first synthesized and used to fabricate the lambda-cyhalothrin/AR (LC/AR) nanoemulsion via in situ phase inverse emulsification, and its properties were then investigated. Results showed that the particle size of the LC/AR nanoemulsion was 50-150 nm with maximum LC loading capacity of as much as 40.9 wt %, high encapsulation efficiency >90%, and great stability in multiple environments. The LC/AR nanoemulsion exhibited better controlled release characteristics compared with LC commercial formulations, and a stronger adhesion on the foliage of the resulted nanoemulsion was also observed, which was attributed to low surface tension and strong interactions with foliar surfaces.

Preparation and Characterization of Controlled-Release Avermectin/Castor Oil-Based Polyurethane Nanoemulsions.

Avermectin (AVM) is a low-toxic and high-active biopesticide, but it can be easily degraded by UV light. In this paper, biodegradable castor oil-based polyurethanes (CO-PU) are synthesized and used as carriers to fabricate a new kind of AVM/CO-PU nanoemulsion through an emulsion solvent evaporation method, and the chemical structure, colloidal property, AVM loading capacity, controlled-release behavior, foliar adhesion, and photostability of the AVM/CO-PU drug delivery systems are investigated. Results show that AVM is physically encapsulated in the CO-PU carrier nanospheres, the diameter of the AVM/CO-PU nanoparticles is <50 nm, and the AVM/CO-PU films are flat and smooth without any AVM aggregate. The drug loading capacity is up to 42.3 wt % with a high encapsulation efficiency of >85%. The release profiles indicate that the release rate is relatively high at the early stage and then slows, which can be adjusted by loaded AVM content, temperature, and pH of the release medium. The foliar pesticide retention of the AVM/CO-PU nanoemulsions is improved, and the photolysis rate of AVM in the AVM/CO-PU nanoparticles is significantly slower than that of the free AVM. A release mechanism of the AVM/CO-PU nanoemulsions is proposed, which is controlled by both diffusion and matrix erosion.

Controlled self-assembly into diverse stimuli-responsive microstructures: from microspheres to branched cylindrical micelles and vesicles.

A series of amphiphilic PDMAEMA-SS-PCL chains with variable ratios of hydrophilic poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) to hydrophobic poly(ε-caprolactone) (PCL) were prepared via ring-opening polymerization, in which the two different moieties were linked via a disulfide bond with reduction responsiveness. After cross-linking by the photodegradable o-nitrobenzyl linkage, the amphiphilic chains could self-assemble into microspheres, branched cylindrical micelles and vesicles, which were responsive to the reduction agent dl-dithiothreitol and UV light irradiation through different mechanisms.

Diffusion Performance of Fertilizer Nutrient through Polymer Latex Film.

Matching the nutrient release rate of coated fertilizer with the nutrient uptake rate of the crop is the best way to increase the utilization efficiency of nutrients and reduce environmental pollution from the fertilizer. The diffusion property and mechanism of nutrients through the film are the theoretical basis for the product pattern design of coated fertilizers. For the coated fertilizer with a single-component nutrient, an extended solution-diffusion model was used to describe the difference of nutrient release rate, and the release rate is proportional to the permeation coefficient and the solubility of the nutrient. For the double- and triple-component fertilizer of N-K, N-P, and N-P-K, because of the interaction among nutrient molecules and ions, the release rates of different nutrients were significantly affected by the components in the composite fertilizer. Coating the single-component fertilizer (i.e., nitrogen fertilizer, phosphate fertilizer, and potash fertilizer) first and subsequently bulk blending is expected to be a promising way to adjust flexibly the nutrient release rate to meet the nutrient uptake rate of the crop.

pH-Triggered Drug Release of Monodispersed P(St-co-DMAEMA) Nanoparticles: Effects of Swelling, Polymer Chain Flexibility and Drug-Polymer Interactions.

Monodispersed pH-sensitive poly(styrene-co-N,N'-dimethylaminoethyl methacrylate) (P(St-co- DMAEMA)) nanoparticles (NPs) were synthesized by emulsion polymerization for use in potential applications in targeted drug delivery to the tumor microenvironment. pH-Sensitive volume swelling and drug release of the NPs with varied St/DMAEMA molar ratios, crosslinking degrees and model drug coumarin-6 loading were explored in vitro to elucidate the pH-sensitive drug release mechanisms. The swelling of the NPs, which accounts for the electrostatic repulsion of protonated tertiary amine groups under acidic conditions, reaches maximum at low pH, low crosslinking density and high DMAEMA content. The NPs undergo a pH-triggered drug release, and under the condition of pH 5 and pH 2, the average release rate during 24 h is 1.5-fold and 3-fold higher than that at physiological pH, respectively. The pH-triggered drug release is related to pH-sensitive swelling, polymer chain flexibility and drug-polymer interaction, and is significantly impacted by the St/DMAEMA molar ratio, degree of crosslinking and drug loading.

Electrostatic-Driven Lamination and Untwisting of ß-Sheet Assemblies.

Peptides or peptide conjugates capable of assembling into one-dimensional (1D) nanostructures have been extensively investigated over the past two decades due to their implications in human diseases and also their interesting applications as biomaterials. While many of these filamentous assemblies contain a ß-sheet-forming sequence as the key design element, their eventual morphology could assume a variety of shapes, such as fibrils, ribbons, belts, or cylinders. Deciphering the key factors that govern the stacking fashion of individual ß-sheets will help understand the polymorphism of peptide assemblies and greatly benefit the development of functional materials from customized molecular design. Herein, we report the decisive role of electrostatic interactions in the lamination and untwisting of 1D assemblies of short peptides. We designed and synthesized three short peptides containing only six amino acids (EFFFFE, KFFFFK, and EFFFFK) to elucidate the effective control of ß-sheet stacking. Our results clearly suggest that electrostatic repulsions between terminal charges reduce the pitch of the twisting ß-sheet tapes, thus leading to highly twisted, intertwined fibrils or twisted ribbons, whereas reducing this repulsion, either through molecular design of peptide with opposite terminal charges or through coassembly of two peptides carrying opposite charges, results in formation of infinite assemblies such as belt-like morphologies. We believe these observations provide important insight into the generic design of ß-sheet assemblies.

Synthesis and characterization of monodispersed P(St-co-DMAEMA) nanoparticles as pH-sensitive drug delivery system.

Monodispersed poly(styrene-co-N,N'-dimethylaminoethyl methacrylate) nanoparticles (P(St-co-DMAEMA) NPs) were synthesized by emulsion polymerization. Zeta potential, volume swelling ratio and in vitro release of fluorescer coumarin-6 from the NPs were determined in buffer of various pH. With an optimized formulation, the diameter of NPs is 100 nm approximately and the polydispersity index (PI) is less than 0.1. The NPs have a hydrophilic surface and alterable surface charge which is almost neutral at normal physiological pH, but becomes much more positive under acidic conditions. The volume swelling ratios and in vitro release of coumarin-6 are highly dependent on pH, which are significantly increased at the lower pH and higher DMAEMA/St molar ratio. More than 70% of the loaded coumarin-6 could be released in 24 h at pH2, which is 2.3-folds higher than that at normal physiological pH. The P(St-co-DMAEMA) NPs show promising applications to targeted drug delivery to tumors.

Influences of MAA on the porous morphology of P(St-MAA) latex particles produced by batch soap-free emulsion polymerization followed by stepwise alkali/acid post-treatment.

Soap-free P(St-MAA) latex particles with variable styrene (St)/methacrylic acid (MAA) ratio were synthesized by batch emulsion copolymerization at 70 degrees C for 7h, and the particles with porous structure were obtained after stepwise alkali/acid post-treatment. The effects of MAA amount on the particle morphologies after the alkali and the stepwise alkali/acid post-treatments were investigated by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Results indicated that the alkali-treated latex particles showed anomalous structure with rough surface, and no hollow was clearly identified inside them. When these alkali-treated particles were further treated with acid solution, the particle surface became much smoother, and porous morphology appeared. It was found that when the MAA amount was less than or equal to 4mol%, no obvious morphological variation was observed; while the latex particles showed clearly porous structure as the MAA amount increased to 6mol%; with the further increase of MAA amount to 8mol%, the pore size decreased distinctly.

Immobilization of aminoglycosidic aminocyclitols antibiotic onto soap-free poly(MMA-EA-AA) latex particles.

Monodispersed soap-free poly(MMA-EA-AA) latex particles with surface carboxyl groups were synthesized by emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and acrylic acid (AA) in aqueous medium, and streptomycin sulfate (SMS) was immobilized onto these particles using three different methods. A model experiment was designed to test the feasibility of the reaction between the carboxyl groups of polymer and the amino groups of the medicine. The covalent coupling between the latex particles and the medicine was confirmed by XPS. Results showed that the medicine molecules were located on the particle surface after immobilization, and the coupling efficiency of SMS in pre-adsorption method was higher than that in direct method. The highest coupling efficiency of this medicine was achieved using the spacer-arm method. It was demonstrated that the immobilized medicine had similar antimicrobial activity as the free form using Escherichia coli as an evaluating organism.

The generation of void morphology inside soap-free P(MMA-EA-MAA) particles prepared by seeded emulsion polymerization.

Monodisperse soap-free P(MMA-EA-MAA) latex particles were synthesized by seeded emulsion polymerization of methyl methacrylate (MMA), ethyl acrylate (EA) and methacrylic acid (MAA), and the particles with void morphology were obtained after undergoing alkali post-treatment. Effects of treatment conditions on particle morphology were investigated. Results showed that the void particles can be obtained under the conditions of the temperature >60 degrees C, initial pH >10.0, treatment time >20 min and 2-butanone amount >2.0 ml. The particle volume and the void size increased to the maximum and then decreased with the increases of initial pH and the treatment time, and these two values increased monotonously with the treatment temperature or 2-butanone amount increased. When the treatment temperature was elevated to 90 degrees C, the treatment time was longer than 180 min, or the 2-butanone amount was more than 8.0 ml, the relatively small voids inside most of the particles combined together to form a large one. The void structure disappeared completely as the initial pH was higher than 12.0. The generation mechanism of the void morphology was discussed.

The properties of covalently immobilized trypsin on soap-free P(MMA-EA-AA) latex particles.

The covalent immobilization of trypsin onto poly[(methyl methacrylate)-co-(ethyl acrylate)-co-(acrylic acid)] latex particles, produced by a soap-free emulsion polymerization technique, was carried out using the carbodiimide method. The catalytic properties and kinetic parameters, as well as the stability of the immobilized enzyme were compared to those of the free enzyme. Results showed that the optimum temperature and pH for the immobilized trypsin in the hydrolysis of casein were 55 degrees C and 8.5, both of which were higher than that of the free form. It was found that K(m) (Michaelis constant) was 45.7 mg . ml(-1) and V(max) (maximal reaction rate) was 793.0 microg . min(-1) for immobilized trypsin, compared to a K(m) of 30.0 mg . ml(-1) and a V(max) of 5 467.5 microg . min(-1) for free trypsin. The immobilized trypsin exhibited much better thermal and chemical stabilities than its free counterpart and maintained over 63% of its initial activity after reusing ten times.