Bis‐clickable Mesoporous Silica Nanoparticles: Straightforward Preparation of Light‐Actuated Nanomachines for Controlled Drug Delivery with Active Targeting

Bis(clickable) mesoporous silica nanospheres (ca. 100 nm) were obtained by the co‐condensation of TEOS with variable amounts (2–5 % each) of two clickable organosilanes in the presence of CTAB. Such nanoparticles could be easily functionalized with two independent functions using the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction to transform them into nanomachines bearing cancer cell targeting ligands with the ability to deliver drugs on‐demand. The active targeting was made possible after anchoring folic acid by CuAAC click reaction, whereas the controlled delivery was performed by clicked azobenzene fragments. Indeed, the azobenzene groups are able to obstruct the pores of the nanoparticles in the dark whereas upon irradiation in the UV or in the blue range, their trans‐to‐cis photoisomerization provokes disorder in the pores, enabling the delivery of the cargo molecules. The on‐command delivery was proven in solution by dye release experiments, and in vitro by doxorubicin delivery. The added value of the folic acid ligand was clearly evidenced by the difference of cell killing induced by doxorubicin‐loaded nanoparticles under blue irradiation, depending on whether the particles featured the clicked folic acid ligand or not.     

A Potential Alternative to Polystyrene: Ring-opening Terpolymerization of Different Epoxides with Phthalic Anhydride Using Metal-free Dual Catalysts

A series of semi-aromatic polyesters named as Poly(PO-CHO-PA) were facilely synthesized via ring-opening terpolymerization of biobased cyclohexane oxide(CHO)/propylene oxide(PO)/phthalic anhydride(PA) using economical U1/PPNCl as dual catalyst. The proportion of CHO-PA and PO-PA segments in polymer can be readily altered by changing the feed ratio of CHO/PO because the reactivity ratios of CHO and PO with PA calculated by Fineman-Ross method are comparable. All synthesized amorphous polyesters with various compositions show one Tg ranging from 62 ℃ to 133 ℃. Significantly, the mechanical, thermal and barrier properties of these amorphous semi-aromatic polyesters are also adjustable and investigated for the first time. The results indicate the semi-polyesters exhibit superior thermostability(T5% ranging from 306 ℃ to323 ℃) and high tensile strength(40.21-55.7 MPa) that is comparable with polystyrene(PS). Furthermore, Poly(PO-CHO-PA) films possess a promising prospect as packaging materials because of its colorless and highly transparent nature, along with low oxygen and water vapor transmission rate. All above performances may guarantee its potential alternative to commercial PS.     

A tridentate CNO‐donor palladium(II) complex as efficient catalyst for direct C―H arylation: Application in preparation of imidazole‐based push–pull chromophores

A series of imidazolium chlorides for the formation of tridentate CNO‐donor palladium(II) complexes featuring N‐heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complexes were prepared by reactions between the ligand precursors and PdCl₂ using K₂CO₃ as base in pyridine with reasonable yields. These air‐stable metal complexes were characterized using ¹H NMR and ¹³C{¹H} NMR spectroscopy and elemental analyses. Heteronuclear multiple bond correlation experiments were performed to identify key NMR signals of these compounds. The structures of two of the complexes were also established by single‐crystal X‐ray diffraction analysis. One of these complexes was successfully applied in the direct C―H functionalization reactions between heterocyclic compounds and aryl bromides, producing excellent yields of coupled products. The coupling reactions were scalable, allowing grams of coupled products to be obtained with a mere 2 mol% of Pd loading. The catalyst system developed allowed the large‐scale preparation of several push–pull chromophores straightforwardly. Photophysical properties based on UV–visible and fluorescence spectroscopy for these chromophores were investigated. Deep blue photoluminescence with moderate quantum efficiency and twisted intramolecular charge transfer excited state were observed for these chromophores. Density functional theory (DFT) and time‐dependent DFT calculations were performed to support the experimental results.     

Colorizing mechanism of brass surface by femtosecond laser induced microstructures

In this paper, we exhibit the colorizing of brass surfaces by forming femtosecond laser induced microstructures on the sample surfaces. A variety of single colors such as brown, yellow, green, and black are introduced on brass surfaces by engineering periodic microgratings, microholes, and ring-shaped micro-patterns using Single Beam Direct Laser Writing (SBDLW) technique. The color of the micro-structured brass surfaces is certainly dependent on the width, depth, and period of the microstructures. Finally, we explain, in brief, the colorizing mechanism of metals by femtosecond laser induced microstructures.     

Generation and Reactivity of a One-Electron-Oxidized Manganese(V) Imido Complex with a Tetraamido Macrocyclic Ligand

The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [Mn^V(TAML)(N-Mes)]⁻ ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC₆H₄)₃N ]^+.[SbCl₆]⁻ and the resulting Mn^VI species readily undergoes H-atom transfer and nitrene transfer reactions.