Combination therapy has been regarded as a promising strategy for cancer treatment due to the enhanced anticancer efficacy achieved by blocking multiple drug resistance pathways. In this work, a drug carrier based on nanoscale ZIF-90 for the codelivery of two anticancer drugs has been synthesized by covalently attaching doxorubicin (DOX) to the surface of ZIF-90 via Schiff base reaction of amino group in DOX and aldehyde group of imidazole-2-carboxaldehyde (ICA) ligand and encapsulating 5-fluorouracil (5-FU) into the pores of the framework. The results of drug loading measurements show that the loading amount of drugs was estimated as high as 36.35 and 11-13.5 wt % for 5-FU and DOX, respectively. Moreover, we demonstrated that the carrier had the potential of cancer-targeted delivery of drugs for the collapse of framework under the pH environment around cancer cells and subsequently releasing drugs. Drug release at pH 5.5, imitating the environment of tumor, can reach over 95%, and the release time is less 16 h, meaning a more effective and faster release of drugs around tumoral cells than that in a normal environment. This is the first report for cancer-targeted codelivery of two different chemical drugs based on nanoscale metal-organic frameworks (NMOFs).
Covalent-organic frameworks (COFs) have been recognized as a new type of promising photocatalysts for hydrogen evolution. To investigate how different functional groups attached in the backbone of COFs affect the overall photocatalytic H 2 evolution, for the first time, we selected and synthesized a series of ketoenamine-based COFs with the same host framework as model system. It includes TpPaÀ COFÀ X (X =À H, À (CH 3 ) 2 , and À NO 2 ) with three different groups attached in the backbone of TpPaÀ COF. We systematically investigated the differences in morphology, light-absorption intensity and band gap of these 2D COFs. The results of photocatalytic H 2 evolution measurements indicate that the TpPaÀ COFÀ (CH 3 ) 2 shows the best activity, while the activity of TpPaÀ COFÀ NO 2 is relatively low compared to that of other two COFs in the system. Moreover, the separation ability of photogenerated charge was also followed the order of TpPaÀ COFÀ (CH 3 ) 2 > TpPaÀ COF > TpPaÀ COFÀ NO 2 . The best photocatalytic H 2 production performance of TpPaÀ COFÀ (CH 3 ) 2 in these systems should be mainly attributed to the better electron-donating ability of À CH 3 groups compared to À H or À NO 2 group, which result in more efficient charge transferring in the inner of the material. This work demonstrates that reasonably adding electrondonating group in TpPaÀ COFs can lead to a better photocatalytic H 2 evolution activity, and which is meaningful for further design of efficient COF-based photocatalysts for H 2 evolution.[a] J.
Cerium and nitrogen codoped TiO 2 photocatalysts were successfully prepared by sol-gel method. The results showed that Ce doped in TiO 2 could prevent phase transition of anatase to rutile and inhibit the growth of crystallite. In addition, Ce and N codoped in TiO 2 enhanced the lattice distortion. N-Ti bond and N-Ti-O bond were formed in codoped titania, which narrowed the energy gap and extended the absorption edge to the visible light range, and the synergistic effects of the Ce and N codoped samples made the red shift more distinct. The results showed that the rate of hydrogen production was the best for the sample prepared under the conditions of the content of Ce doped for 0.6% (molar ratio) and calcination temperature of photocatalyst preparation at 500°C.
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