The reaction between 1,3,5-benzenetribenzoic acid (H 3 BTB) and In(NO 3 ) 3 hydrate in diethylformamide yielded a new In III -metal-organic framework, [(CH 3 CH 2 ) 2 NH 2 ] 3 [In 3 (BTB) 4 ]•10DEF•14H 2 O (I). The countercation and solvent-free doubly interpenetrated I potentially contains 71.0% of solvent accessible void. Although the framework of I was not stable enough to maintain its original structure when the solvent molecules were removed, the as-prepared I was found to be a very good sorbent for acridine orange hydrochloride, a large Reichardt's dye, and hydrophobic iodine molecule in solution. The as-prepared I exhibited increased uptake amount in the order of Reichardt's dye > acridine orange hydrochloride > iodine. The largest uptake of the bulky Reichardt's dye by I could be attributed to the optimized structural fitting of Reichardt's dye into the large threedimensional void space of I. The structure of Reichardt's dye-encapsulated I_RD was unambiguously revealed by X-ray crystallography for the first time.
We prepared cell membrane-permeable hollow mesoporous silica capsules (HMSCs) by a simple new method. CTAB micellar assembly in cholesterol emulsion gave rise to a novel capsular morphology of the HMSC particles. The HMSCs consisted of mesostructured silica walls with a large surface hole (25-50 nm) and the average particle dimension was 100-300 nm. They exhibited high surface areas of up to 719.3 m(2) g(-1) and a mesoporous range of pores of 2.4-2.7 nm. The surface-functionalized HMSCs could also be prepared by a similar co-condensation method using tetraethoxysilane with various organoalkoxysilane precursors in the presence of cholesterol. These organically modified HMSCs could be further modified on demand. For example, a carboxy-functionalized HMSC could be surface-functionalized by a green fluorescent 5-aminofluorescein (AFL) through an amidation reaction to afford a fluorescent AFL-HMSC. The hollow capsular morphology of the HMSCs with a large surface hole enabled us to develop very efficient intracellular delivery systems for membrane-impermeable ions, molecules, and various functional proteins. Non-covalent sequestration and delivery of proteins as well as covalent linkage of fluorescent molecules on the silica surface are effective for this system. The highly negatively charged green fluorescent probe mag-fluo-4 could be intracellularly delivered into HeLa cells by HMSC without any difficulty. The HMSCs could also effectively transport large functional proteins such as antibodies into HeLa cells. The efficiency of protein delivery by HMSC seems to be 3-22-fold higher than that of mesoporous silica nanospheres (MSNs) based on confocal laser scanning microscopy (CLSM) analysis.
To simply reduce HAuCl(4) using 2-thiophenemethanol in an aqueous solution at room temperature, a novel metallic Au nanostructure with a high SERS activity was obtained. Flat sheet-like Au nanoleaves possessing many nanogap hotspots bound with a large percentage of high-index facets were obtained.
A CO2 selective dynamic two-dimensional (2D) MOF system, [Zn(glu)(μ-bpe)]·2H2O (·2H2O) (glu = glutarate, bpe = 1,2-bis(4-pyridyl)ethylene), is prepared. Based on variable temperature PXRD patterns, I·2H2O exhibits a structural transformation of the framework upon desolvation. Various gas sorption analyses at low temperatures reveal that solvent-free I selectively adsorbs CO2 over N2, H2, and CH4. Stepped CO2 isotherms for solvent-free I with a large hysteresis between adsorption and desorption branches at 196 K indicate that I is a dynamic framework. Moreover, I·2H2O shows efficient heterogeneous catalytic reactivity for transesterification of various esters. The catalyst can be recycled multiple times without losing its original activity.
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