Endosomal pH-activatable doxorubicin (DOX) prodrug nanogels were designed, prepared, and investigated for triggered intracellular drug release in cancer cells. DOX prodrugs with drug grafting contents of 3.9, 5.7, and 11.7 wt % (denoted as prodrugs 1, 2, and 3, respectively) were conveniently obtained by sequential treatment of poly(ethylene glycol)-b-poly(2-hydroxyethyl methacrylate-co-ethyl glycinate methacrylamide) (PEG-b-P(HEMA-co-EGMA)) copolymers with hydrazine and doxorubicin hydrochloride. Notably, prodrugs 1, 2, and 3 formed monodispersed nanogels with average sizes of 114.4, 75.3, and 66.3 nm, respectively, in phosphate buffer (PB, 10 mM, pH 7.4). The in vitro release results showed that DOX was released rapidly and nearly quantitatively from DOX prodrug nanogels at endosomal pH and 37 °C in 48 h, whereas only a minor amount (ca. 20% or less) of drug was released at pH 7.4 under otherwise the same conditions. Confocal laser scanning microscope (CLSM) observations revealed that DOX prodrug nanogels delivered and released DOX into the cytosols as well as cell nuclei of RAW 264.7 cells following 24 h incubation. MTT assays demonstrated that prodrug 3 had pronounced cytotoxic effects to tumor cells following 72 h incubation with IC(50) data determined to be 2.0 and 3.4 μg DOX equiv/mL for RAW 264.7 and MCF-7 tumor cells, respectively. The corresponding polymer carrier, PEG-b-P(HEMA-co-GMA-hydrazide), was shown to be nontoxic up to a tested concentration of 1.32 mg/mL. These endosomal pH-activatable DOX prodrug nanogels uniquely combining features of water-soluble macromolecular prodrugs and nanogels offer a promising platform for targeted cancer therapy.

Hydrophilic honeycomb films are directly fabricated by the self-assembly of complexes of polylacticacid and dodecyl trimethyl ammonium chloride in ‘breath figure’ templating. The presence of a cationic surfactant not only improves film regularity, but also imparts them with excellent wettability.

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Bioinspired honeycomb-like porous films with switchable properties have drawn much attention recently owing to their potential application in scenarios in which the conversion between two opposite properties is required. Herein, the CO 2 -gastriggered ON/OFF switching wettability of biocompatible polylactic acid (PLA) honeycomb porous films is fabricated. Highly ordered porous films with diameters between 2.0 and 2.8 μm are separately prepared from complexes of nonresponsive PLA and a CO 2 -sensitive melamine derivative [N 2 ,N 4 ,N 6 -tris(3-(dimethylamino)propyl)-1,3,5-triazine-2,4,6-triamine, MET] via the breath figure method. The hydrophilic CO 2 -sensitive groups can be precisely arranged in the pore's inner surface and/or top surface of the films by simply changing the PLA/MET ratio. The sensitive groups in the pore's inner surface act as a switch triggered by CO 2 gas controlling water to enter the pores or not, thus resulting in ON/OFF switching wettability. The largest response of the water contact angle of honeycomb films reaches 35°, from 100 to 65°, leading to an obvious hydrophobic−hydrophilic conversion. The improved surface wettability enhances the interaction between the cell and honeycomb film surface, thus resulting in a better cell attachment. Such smart properties accompanying the biocompatible polymer and biological gas trigger facilitate possible biomedical and bioengineering applications in the future for these films.

Surfactant flooding plays a critical role in chemically enhanced oil recovery over the last half century, with the widely accepted mechanism of ultralow interfacial tension (IFT) by forming middle-phase microemulsions with high concentration of a lead surfactant and a cosurfactant. However, it is found practically from field trials that high oil recovery efficiency can be obtained from low concentration surfactant flooding without forming microemulsions, and the principle behind has not been clearly unraveled yet. Here the solubilization of paraffin oil by the micelles formed with a commercial enhanced oil recovery surfactant, raw naphthenic arylsulfonates (NAS), was investigated using ultraviolet-visible (UV-Vis) spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM). It is found that paraffin oil can be well solubilized inside the NAS micelles, and mainly localized in the hydrophobic core of the micelles. The solubilization capacity of NAS micelles increases with increasing its concentration, and the size of micelles increases, but morphology of the micelles remains spherical with increasing the amount of paraffin oil, along with an appearance transition from transparent to opaque until the maximum solubilization capacity is reached. Core flooding results with crude oil indicate that in the presence of 0.24 wt.% polymer, addition of 0.1, 0.2, 0.5, and 1.0 wt.% NAS can get oil recovery factor of 24.1%, 27.0%, 30.5%, and 38.3%, which increases linearly with increasing NAS concentration though with the interfacial tension values only in the magnitude of 10 −2 mN m −1 level. These findings prove preliminarily micellar solubilization can help increasing oil recovery efficiency even without ultralow IFT.