The effect of flow partition on storm runoff and pollutant retention through raingardens with and without subsurface drainage.

Green infrastructures (GIs) have been advocated worldwide to mitigate the negative impact of urbanization on regional hydrological cycle, their functions are closely related to their design features and the local environmental condition. This paper reports a field monitoring study that aimed to investigate how runoff partition in raingardens would affect flow and pollutant retention. A paired field experiment was conducted to compare runoff and pollutant retentions in two raingardens with and without subsurface drainage in a shallow water table area. Concentrations of ammonia nitrogen (NH3-N), nitrate nitrogen (NO3-N) and total phosphorus (TP) were measured at raingarden inflow, overflow and drainage paths. The results from 28 monitored storm events over two years showed that the raingarden without subsurface drainage achieved its retention mainly through ponding and infiltration, its pollutant retention rates (76% for TP, 81% for NO3-N, and 79% for NH3-N) were higher than its runoff retention rate (61%), indicating a first flush effect on pollutants retention in the raingarden during storm events, especially when the raingarden was empty and dry. The raingarden with subsurface drainage facilitated quick discharge of water, the observed runoff reduction through the raingarden was 36%; pollutant removal rates were quite variable: NH3-N was removed by 91% while the NO3-N and TP were increased by 3-47%. These results suggest that facilitating specific processes for targeted pollutants is necessary for achieving substantial pollutant removal in a stormwater retention device. Subsurface drainage pipes resulted in short circulating of runoff and lowered pollutant removal rates in the raingarden. Considering the water table fluctuation during the experimental period, we recommend to build infiltration-based GI devices to better capture first flush in intensively developed urban area, which caused deeper groundwater table. In conclusion, installations of different GI devices in urban landscape need to consider the local environmental conditions and facilitate the design features to meet specific storm runoff and pollutants mitigation requirement.

Compositional tuning of epoxide-polyetheramine "click" reaction toward cytocompatible, cationic hydrogel particles with antimicrobial and DNA binding activities.

UNLABELLED: The "click" characteristics of nucleophilic opening of epoxide have recently been exploited for the development of a functional hydrogel particle system based on commercially available bisepoxide and triamine polyetheramine monomers. Key features of these particles include high cationic charges and responsiveness to temperature, pH, and oxidation. Despite these advantages, the cytocompatibility of these particles must be considered prior to use in biomedical applications. Here we demonstrate that, by introducing a diamine polyetheramine as a comonomer in the "click" reaction, and tuning its molar ratio with the triamine monomer, cationic nanoparticles with improved cytocompatibility can be prepared. The reduced cytotoxicity is primarily due to the hydrophilic backbone of the diamine comonomer, which has polyethylene glycol as a primary component. The resulting nanoparticles formed from the diamine comonomer exhibited a lower surface charge, while maintaining a comparable size. In addition, the responsiveness of the nanoparticles to temperature, pH, and oxidation was conserved, while achieving greater colloidal stability at basic pH. Results from this study further demonstrated that the nanoparticles were able to encapsulate Nile red, a model for hydrophobic drug molecules, were effective against the bacteria Staphylococcus aureus, and were capable of binding DNA through ionic complexation. Based on the results from this work, the use of diamine comonomers significantly reduces the cytotoxicity of similarly developed hydrogel nanoparticles, allowing for numerous biomedical applications, including nanocarriers for therapeutic agents with poor water solubility, treatment of bacterial infection, and non-viral vectors for gene therapy. STATEMENT OF SIGNIFICANCE: In recent years significant attention has been placed on the development of nanocarriers for numerous biomedical applications. Of particular interest are cationic polymers, which contain high positive surface charges that allow binding of numerous therapeutic agents. Unfortunately, the advantages of cationic polymers for binding, are often negated by the tendency of these polymers to be cytotoxic. Previous studies have developed highly responsive cationic hydrogel nanoparticles, which meet several of the criteria for biomedical applications, but were acutely cytotoxic. In this work, cationic hydrogel nanoparticles, with significantly improved cytocompatibility, were synthesized using simple, green epoxy chemistry. In addition, the ability of these nanoparticles to maintain a small size (<500nm), bind DNA, encapsulate hydrophobic drugs, and kill bacteria was maintained.

Facile Use of Cationic Hydrogel Particles for Surface Modification of Planar Substrates Toward Multifunctional Neural Permissive Surfaces: An in Vitro Investigation.

Synthetic materials such as silicon have been commonly used for neural interfacing applications but are intrinsically noninteractive with neurons. Here, a facile approach has been developed to integrate both chemical and topographical cues to impart neural permissiveness for such materials. The approach simply exploits the basic phenomenon of electrostatically driven adsorption of colloidal particles onto a solid material and applies it to a cationic hydrogel particle system that we have developed recently based on "click" reaction of epoxide and amine. The particle adsorption process can be tuned by varying the adsorption time and the concentration of the original colloidal suspension, both of which directly control the surface densities of the adsorbed hydrogel particles. Using the PC12 cell line and primary cortical neurons derived from chick embryo, we demonstrate that the particle-adsorbed surface readily supports robust cell adhesion and differentiation. Although the extent of neural permissiveness exhibited by such particle-adsorbed surface was comparable to the cationic polyethylenimine-coated control surface, the adsorbed hydrogel particles offer a unique reservoir function to the modified surface that is unparalleled by the control. The successful loading of hydrophobic dye of nile red to the surface adsorbed hydrogel particles indicates that the modified surface not only provides physical support of neurons, but also can be explored in the future to exert localized therapeutic actions favorable for neural interfacing.

Water-based synthesis of cationic hydrogel particles: effect of the reaction parameters and in vitro cytotoxicity study.

Micro/nanoscale hydrogel particles are of great interest for biomedical applications, such as carriers for therapeutic delivery. Compared to conventional hydrogel particles that are mainly composed of vinylic monomers, we have introduced a simple methodology to prepare multi-functional cationic hydrogel particles by adopting the epoxy-amine chemistry in water exemplifying "click" characteristics. Herein, we investigate the effects of key reaction parameters, including time, temperature, reactant concentration and amine-epoxy stoichiometric ratio, on the preparation and properties of such hydrogel particles. Our results indicated that the aforementioned parameters could greatly impact the particle formation. The hydrodynamic diameter, surface charge, and morphology of the resultant particles were characterized by dynamic light scattering and scanning electron microscopy. Particle size was inversely correlated with the following reaction parameters: reaction time, temperature, and reactant concentration. This is likely due to the influence of the parameters on the formation of the intermediate thermosensitive prepolymers. Different reaction conditions yielded a wide range of particle surface charges, varying from +47 mV to +71 mV. Morphological analysis also revealed significant effects induced by the variation of reaction time and temperature. All particles exhibited a temperature-dependent swelling property. However, the extent of swelling and sensitivity varied depending on the reaction conditions. Finally, in vitro cytocompatibility studies based on murine RAW264.7 macrophages showed the particle acute cytotoxicity being dose and surface charge dependent. Cytocompatibility of the cationic hydrogel particles was improved by reducing the surface charges with variation of the synthesis conditions.

Agarose hydrogels embedded with pH-responsive diblock copolymer micelles for triggered release of substances.

Hybrid agarose hydrogels embedded with pH-responsive diblock copolymers micelles were developed to achieve functional hydrogels capable of stimulus-triggered drug release. Specifically, a well-defined poly(ethylene oxide) (PEO)-based diblock copolymer, PEO-b-poly(2-(N,N-diisopropylamino)ethyl methacrylate) (PEO(113)-b-PDPAEMA(31), where the subscripts represent the degrees of polymerization of two blocks), was synthesized by atom transfer radical polymerization. PDPAEMA is a pH-responsive polymer with a pKa value of 6.3. The PEO(113)-b-PDPAEMA(31) micelles were formed by a solvent-switching method, and their pH-dependent dissociation behavior was investigated by dynamic light scattering and fluorescence spectroscopy. Both studies indicated that the micelles were completely disassembled at pH = 6.40. The biocompatibility of PEO(113)-b-PDPAEMA(31) micelles was demonstrated by in vitro primary cortical neural culture. Hybrid agarose hydrogels were made by cooling 1.0 wt % agarose solutions that contained various amounts of PEO(113)-b-PDPAEMA(31) micelles at either 2 or 4 °C. Rheological measurements showed that the mechanical properties of gels were not significantly adversely affected by the incorporation of diblock copolymer micelles with a concentration as high as 5.0 mg/g. Using Nile Red as a model hydrophobic drug, its incorporation into the core of diblock copolymer micelles was demonstrated. Characterized by fluorescent spectroscopy, the release of Nile Red from the hybrid hydrogel was shown to be controllable by pH due to the responsiveness of the block copolymer micelles. Based on the prominent use of agarose gels as scaffolds for cell transplantation for neural repair, the hybrid hydrogels embedded with stimuli-responsive block copolymer micelles could allow the controlled delivery of hydrophobic neuroprotective agents to improve survival of transplanted cells in tune with signals from the surrounding pathological environment.

Facile aqueous-phase synthesis of multi-responsive nanogels based on polyetheramines and bisepoxide.

A new strategy for the preparation of nanogels from commercially available monomers of bisepoxide and aliphatic polyetheramine has been developed. The nanogels are generated in a one-pot process through aggregation polymerization of an in situ formed thermal sensitive intermediate polymer in an additive-free and catalyst-free aqueous environment. Such a facile process allows easy size tuning of the gel particles from the nanometer to the micron scale, simply by adjusting the reactant concentration. The obtained nanogels demonstrated responsiveness to multiple biologically relevant stimuli, including temperature, pH, and oxidation. Nile red was encapsulated in the nanogels as a model hydrophobic drug. In vitro drug release studies showed stimuli-triggered release from the nanogels, suggesting the potential for controlled drug delivery.