In situ synthesis of Ti^(3+) self-doped mesoporous TiO_2 as a durable photocatalyst for environmental remediation

This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.

Efficient hydrolysis of cellulose to glucose catalyzed by lignin-derived mesoporous carbon solid acid in water

Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.

Supramolecular-templated synthesis of mesoporous silica-zirconia nanocomposite

Mesoporous SiO2-ZrO7 nanocomposite was successfully prepared by using supramolecular tfiblock copolymer as the template through evaporation-induced self-assembly approach. The textural and structural properties were characterized by X-ray diffraction, nitrogen adsorption analysis, and transmission electron microscope. Comparison between pure mesoporous silica and mesoporous silica-zirconia nanocomposite was also presented in this work. The surface area, pore size, and pore volume decreased as the Zr doping in the mesoporous silica framework. But the obtained nanocomposite maintained the cubic Im3m-type mesoporous structure.

Selectively enhancing radiosensitivity of cancer cells via in situ enzyme-instructed peptide self-assembly

The radiotherapy modulators used in clinic have disadvantages of high toxicity and low selectivity.For the first time,we used the in situ enzyme-instructed self-assembly(EISA)of a peptide derivative(Nap-GDFDFpYSV)to selectively enhance the sensitivity of cancer cells with high alkaline phosphatase(ALP)expression to ionizing radiation(IR).Compared with the in vitro pre-assembled control formed by the same molecule,assemblies formed by in situ EISA in cells greatly sensitized the ALPhigh-expressing cancer cells to y-rays,with a remarkable sensitizer enhancement ratio.Our results indicated that the enhancement was a result of fixing DNA damage,arresting cell cycles and inducing cell apoptosis.Interestingly,in vitro pre-formed assemblies mainly localized in the lysosomes after incubating with cells,while the assemblies formed via in situ EISA scattered in the cell cytosol.The accumulation of these molecules in cells could not be inhibited by endocytosis inhibitors.We believed that this molecule entered cancer cells by diffusion and then in situ self-assembled to form nanofibers under the catalysis of endogenous ALP.This study provides a successful example to utilize intracellular in situ EISA of small molecules to develop selective tumor radiosensitizers.

Effect of reduction-oxidation treatment on structure and catalytic properties of ordered mesoporous Cu-Mg-Al composite oxides

Ordered mesoporous Cu-Mg-A1 composite oxides were synthesized via the one-pot evaporation-in- duced self-assembly strategy. Using this method, copper was first homogeneously incorporated into the ordered mesoporous spinel matrix. After H2 reduction treatment, according to X-ray diffraction （XRD） and transmission electron microscopy （TEM） results, copper existed as metallic nanoparticles with the size of 6-10 nm that well decorated the parent mesoporous skeleton. The metallic nanoparticles were then re-oxidized to copper oxide when exposed to air or during CO oxidation reaction at low temperatures. Thus, copper migrated from bulk spinel phase to the surface after the reduction-oxidation treat- ment. Moreover, the copper on the surface was re-incor- porated into the bulk spinel phase by further thermal treatment at much higher temperature in the presence of air. The correlation between the state of copper in the mesoporous composite oxides and the catalytic perfor- mance toward CO oxidation was studied. It was found that copper existed as oxide nanoparticles on the surface of mesoporous Mg-Al skeleton is much more active than that existed as lattice Cu ions in spinel phase.