Mitochondria-Targeting Polymer Micelles in Stepwise Response Releasing Gemcitabine and Destroying the Mitochondria and Nucleus for Combined Antitumor Chemotherapy.

Mitochondrial DNA and nuclear DNA are essential genetic material which play an important role in maintaining normal metabolism, survival, and proliferation of cells. Constructing a mitochondria-targeting stimuli-responsive nano-drug delivery system releasing chemotherapeutic agents in a stepwise response manner and destroying mitochondrial DNA and nuclear DNA simultaneously is an effective way to improve the anti-tumor effect of chemotherapeutic agents. In this study, a new mitochondria-targeting pH/ROS dual-responsive block copolymer TPP-PEG2k-b-(BS-AA)n (P1), untargeted pH/ROS dual-responsive copolymer mPEG2k-b-(BS-AA)n (P2), pH single-responsive copolymer (mPEG2k-b-(AH-AA)n (P3), ROS single-responsive copolymer mPEG2k-b-(SA-TG)n (P4), and non-responsive copolymer mPEG-b-PCL (P5) were constructed. pH/ROS-responsive properties were characterized by proton nuclear magnetic resonance (1H NMR) and dynamic light scattering (DLS). Anticancer chemotherapeutic agent gemcitabine (GEM) or fluorescent substance Nile Red (NR) were loaded in the polymer micelles. Results of the mitochondrial colocalization experiment indicate that (5-carboxypentyl)(triphenyl)phosphonium bromide (TPP)-functionalized P1 micelles could be efficiently targeted and located in mitochondria. Results of the cellular uptake experiment showed that pH/ROS dual-responsive GEM-loaded P1 and P2 micelles have faster internalized and entry nucleus rates than single-responsive or non-responsive GEM-loaded micelles. The in vitro release experiment suggests pH/ROS dual-responsive GEM/P1 and GEM/P2 micelles have higher cumulative release than single-responsive GEM/P3 and GEM/P4 micelles. The in vitro cytotoxic experiment shows that the mitochondria-targeted dual-responsive GEM/P1 micelles had the lowest IC50 values, and the cytotoxic effect of dual-responsive GEM/P2 micelles was superior to the single-responsive and non-responsive drug-loaded micelles.

Efficient purification with high recovery of vanadium bromoperoxidase from Corallina officinalis.

A novel, simple and highly efficient process for purifying vanadium bromoperoxidase from Corallina officinalis is reported. The key innovation is adding 0.5 mM sodium orthovanadate to the crude cell extract followed by heating at 70°C for 2 h, by which a 5.4-fold purification with a 100% activity recovery was achieved. Combining the heat treatment with ammonium sulfate precipitation and DEAE-52 column chromatography, the overall yield was 84%, 3.8 times greater than the highest yield previously reported. Finally, a specific activity of 310 U/mg, a 27-fold purification of the crude enzyme solution was produced.

A Facile Method to Control Pore Structure of PVDF/SiO2 Composite Membranes for Efficient Oil/Water Purification.

The use of poly(vinylidene fluoride) (PVDF) microfiltration (MF) membranes to purify oily water has received much attention. However, it is challenging to obtain high-performance PVDF microfiltration membranes due to severe surface fouling and rapid decline of permeability. This study explored a new approach to fabricate high-performance PVDF/silica (SiO2) composite membrane via the use of a polymer solution featuring lower critical solution temperature (LCST) characteristics and the non-solvent thermally induced phase separation method (NTIPS). Coupling with morphological observations, the membrane formation kinetics were analyzed in depth to understand the synergistic effect between the LCST solution properties and fabrication conditions in NTIPS. Utilizing such a synergistic effect, the transition from finger-like macrovoid pores to bi-continuous highly connected pores could be flexibly tuned by increasing the PVDF concentration and the weight ratio of SiO2/PVDF in the dope solution and by raising the coagulation temperature to above the LCST of the solution. The filtration experiments with surfactant-stabilized oil-water emulsion showed that the permeation flux of the PVDF/SiO2 composite membranes was higher than 318 L·m-2·h-1·bar-1 and the rejection above 99.2%. It was also shown that the PVDF/SiO2 composite membranes, especially those fabricated above the LCST, demonstrated better hydrophilicity, which resulted in significant enhancement in the anti-fouling properties for oil/water emulsion separation. Compared to the benchmark pure PVDF membrane in oily water purification, the optimal composite membrane T70 was demonstrated via the 3-cycle filtration experiments with a significantly improved flux recovery ratio (Frr) and minimal reduced irreversible fouling (Rir). Overall, with the developed method in this work, facile procedure to tune the membrane morphology and pore structure was demonstrated, resulting in high performance composite membranes suitable for oil/water emulsion separation.

Phthalate exposure and cumulative risk in a Chinese newborn population.

Phthalates have been attracted as a considerable attention in toxicological research as well as public health context due to their ubiquitous occurrence and potential adverse health effects. Newborns are susceptible to the environmental risk factors; however, data are still limited on newborn phthalate exposure and risk assessment worldwide, especially in China. This study was nested in a cross-sectional retrospective study of 1359 pregnant women recruited in Xiamen Maternity and Child Care Hospital, China, during June to July 2012. All urine samples from newborn were collected using disposal diapers during the first two postnatal days, and seven phthalate metabolites were measured by LC-ESI-MS/MS. Phthalate exposure and accumulation risk were evaluated based on the measured newborn urinary internal doses. The detection rate (96.5%) and the median concentration (17.5 ng/mL) of mono-n-butyl phthalate (MBP) were the highest, while monobenzyl phthalate (MBzP) concentration was the lowest with a detection rate (1.50%). By estimating the daily intakes of the parent phthalates, their EDI were 0.04, 0.10, 0.32, 0.00, and 0.12 µg/kg-bw/day for dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalates (DBP), benzyl butyl phthalate (BBzP), and di-(2-ethylhexyl) phthalate (DEHP), respectively. The newborns were commonly exposed to phthalates but no one exceeds the regulated tolerable daily intake (TDI) values in this large newborn population.

Performance and Fouling Study of Asymmetric PVDF Membrane Applied in the Concentration of Organic Fertilizer by Direct Contact Membrane Distillation (DCMD).

This study proposes using membrane distillation (MD) as an alternative to the conventional multi-stage flushing (MSF) process to concentrate a semi-product of organic fertilizer. By applying a unique asymmetric polyvinylidene fluoride (PVDF) membrane, which was specifically designed for MD applications using a nonsolvent thermally induced phase separation (NTIPS) method, the direct contact membrane distillation (DCMD) performance was investigated in terms of its sustainability in permeation flux, fouling resistance, and anti-wetting properties. It was found that the permeation flux increased with increasing flow rate, while the top-surface facing feed mode was the preferred orientation to achieve 25% higher flux than the bottom-surface facing feed mode. Compared to the commercial polytetrafluoroethylene (PTFE) membrane, the asymmetric PVDF membrane exhibited excellent anti-fouling and sustainable flux, with less than 8% flux decline in a 15 h continuous operation, i.e., flux decreased slightly and was maintained as high as 74 kg·m-2·h-1 at 70 °C. Meanwhile, the lost flux was easily recovered by clean water rinsing. Overall 2.6 times concentration factor was achieved in 15 h MD operation, with 63.4% water being removed from the fertilizer sample. Further concentration could be achieved to reach the desired industrial standard of 5x concentration factor.

Preparation and Characterization of Hydrophilically Modified PVDF Membranes by a Novel Nonsolvent Thermally Induced Phase Separation Method.

In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance Rt of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties.

Porous titania/carbon hybrid microspheres templated by in situ formed polystyrene colloids.

A new strategy to synthesize hierarchical, porous titania/carbon (TiO2/C) hybrid microspheres via solvothermal reaction in N,N'-dimethyl formamide (DMF) has been developed. In situ formed polystyrene (PS) colloids have been used as templating agent and carbon source, through which TiO2/PS microspheres with a diameter of ca. 1 µm are built by packed TiO2 nanoparticles of tens of nanometers. The TiO2/PS microspheres are converted to TiO2/C microspheres with different amounts of carbon under controlled calcination condition. The mechanism investigation unveils that the introduction of concentrated HCl creates surface tension between PS and DMF, leading to the formation of PS colloids in solution. The solvothermal treatment further promotes the formation of PS colloids and integration of the titania nanoparticles within the PS colloids. The morphology, crystallinity, nature and content of carbon, UV-Vis absorption, carbon doping, pore size distribution, pore volume, and BET surface area of the TiO2 microspheres with different amounts of carbon have been measured. The applications of the TiO2/C hybrid microspheres as photo catalyst for water splitting and lithium-ion battery anode have been demonstrated. Superior photo catalytic activity for hydrogen conversion under both full spectrum and visible light illumination compared to commercial P25 has been observed for the TiO2/C microspheres with 2 wt% of carbon. Besides, the TiO2/C microspheres with 8 wt% of carbon as lithium-ion battery anode showed a much higher capacity than the bare TiO2 microsphere anode. The origin for the enhanced performance as photo catalyst and lithium-ion battery anode is discussed.