A co-assembly process for high strength and injectable dual network gels with sustained doxorubicin release performance.

Adopting a non-covalent co-assembly strategy shows great potential in loading drugs efficiently and safely in drug delivery systems. However, finding an efficient method for developing high strength gels with thixotropic characteristics is still challenging. In this work, by hybridizing the low molecular weight gelator fluorenylmethyloxycarbonyl-phenylalanine (Fmoc-F) (first single network, 1st SN) and alginate (second single network, 2nd SN) into a dual network (DN) gel, gels with high strength as well as thixotropy were prepared efficiently. The DN gels showed high strength (103 Pa in SN gels and 105 Pa in DN gels) and thixotropic characteristics (yield strain <25%; recovery ratio >85% within 100 seconds). The application performance was verified by loading doxorubicin (DOX), showing better encapsulation capacity (77.06% in 1st SN, 59.11% in 2nd SN and 96.71% in DN) and sustained release performance (lasting one week under physiological conditions) than single network gels. Experimental and DFT results allowed the elaboration of the specific non-covalent co-assembly mechanism for DN gel formation and DOX loading. The DN gels were formed by co-assembly driven by H-bond and π-π stacking interactions and then strengthened by Ca2+-coupling. Most DOX molecules co-assembled with Fmoc-F and alginate through π-π stacking and H-bond interactions (DOX-I), with a few free DOX molecules (DOX-II) left. Proven by the release dynamics test, DOX was released through a diffusion-erosion process, in an order of DOX-I first and then DOX-II. This work suggests that non-covalent co-assembly is a useful technique for effective material strengthening and drug delivery.

Possible enrichment process of Cd in the Se-rich soil area of Lanshan District, Shandong Province, China.

High cadmium (Cd) concentrations widely occured in selenium (Se)-rich soils, which has been an important obstacle in the usage of Se-rich soils. There is still no special information detailing the enrichment process and mechanism of Cd in Se-rich soils. 4474 soils and 21 rocks in Lanshan District were sampled to detect its enrichment process. The surface soils have Cd concentrations of 0.01-9.41 mg·kg-1 (an average of 0.16 mg·kg-1). The soil Cd concentrations were significantly correlated with soil Se concentrations. The relatively higher-Cd surface soils are distributed in Lower-middle Ordovician carbonate areas with Se-rich soils and Quaternary areas with typical anthropic activities. Surface soils in Ordovician carbonate area have the highest Cd concentrations. Soil Cd concentrations are significantly correlated with sulfophil elements (Zinc (Zn), Copper (Cu), Molybdenum (Mo), Lead (Pb) and Arsenic (As) etc.), Ca (Calcium) concentrations and soil organic carbon (SOC). The soil and rock samples from different geological units also confirmed soil Cd concentrations developing from Ordovician carbonates were higher than those from other rocks. The results indicate the soil Cd concentrations were the complex consequences of bedrock, soil-forming processes and anthropogenic activities. Higher Ca concentrations and more reduction environments result in high-Cd bedrock. CaCO3 leaching and alkaline pH, which are the special soil-forming process of carbonates, enrich Cd in soils. Agricultural and industrial activities also affect soil Cd concentrations. An enrichment model of Cd in Se-rich soils is forwarded.

Ground water copper levels in the seawater intrusion area and the possible physical and chemical dynamics.

Seawater intrusion, a common geological process along the coastal zones, changes the groundwater properties, which are potentially associated with the groundwater copper (Cu) levels. However, there are no studies on the details of groundwater Cu levels affected by seawater intrusion. The groundwater in the seawater intrusion area of Buzhuang Town was sampled to detect the effect of seawater intrusion on groundwater Cu levels. The Cu levels in the local groundwater range between 0.92 and 4.99 µg L-1, which averages about 5 times than those in the non-intrusion area. The Cu deviations (ΔCu) are positive, and increase with more intrusion of seawater. Simulation experiments also confirm that more Cu leaches from sediments when more seawater or brine water is mixed in. The groundwater Cu levels are positively correlated with TDS, Cl-, Br-, SO42-, HCO3-, Na+, K+ and Mg2+. The Cu-bearing minerals in the local groundwater are under-saturated. The CEC of the sediment for the simulated experiments decreases with more mixture of seawater or brine water. CuCO03, Cu(OH)02, CuHCO3+, Cu(CO3)22-, CuCl2-, Cu2+ species in the local groundwater are obviously higher than those in the non-intrusion area, and the levels of CuCl2-, Cu+, CuCO3, Cu2+, CuSO4, CuOH+, CuCl+, Cu2(OH)22+ are positively correlated with the degree of seawater intrusion, indicating the important role of Cl-, HCO3-, OH- complexation on groundwater Cu levels. Thus, ion competition and complexation are the important dynamics of groundwater Cu enrichment along the coastal zones. A new enrichment model of groundwater Cu in the seawater intrusion area is presented. Seawater intrusion should be taken into consideration when the enrichment mechanisms of groundwater Cu are discussed.