ABSTRACT
Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with six NH···O bonds (d(N···O) = 2.857 (3) to 3.092 (3) Å) and one OH···O bond (d(O···O) = 2.57 (2) Å) from three receptors; however, in solution the anion is bound within the pseudo-cavity of one receptor.
Subject(s)
Chemistry, Organic , Coordination Complexes/chemical synthesis , Sulfates/chemistry , Anions/chemistry , Coordination Complexes/metabolism , Crystallography, X-Ray , Hydrogen Bonding , Magnetic Resonance Spectroscopy , Models, Molecular , Molecular Mimicry , Molecular Structure , Periplasmic Binding Proteins/chemistry , Periplasmic Binding Proteins/metabolism , Solutions , Sulfates/metabolism , Urea/chemistryABSTRACT
A pH-responsive, TiO2-attached sensitizer was prepared based on the adsorption of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin (TCPP) onto TiO2 nanoparticles. This colloidally dispersed TiO2-attached TCPP behaves as a single-phase colloidal sensitizer at pH 1.0-3.3 with quantum yields of singlet oxygen production (Phi(Delta)) between 0.20 and 0.25, as a heterogeneous particle sensitizer at pH 3.5-6.0 with Phi(Delta) between 0.25 and 0.50, and as homogeneous free TCPP molecules in alkaline solutions with Phi(Delta) = 0.53. The changes in Phi(Delta) are fully consistent with pH-dependent adsorption of TCPP onto the TiO2 surface. Recovery yields of 99.8% for TCPP and 98.8% for TiO2 were obtained from 1.4 mM TiO2-attached TCPP. We attribute its photosensitization ability to retaining TCPP solubility on the TiO2 surface and, hence, activity. This novel system shows a potential to bridge the gap between easily recoverable and highly efficient sensitizers.
Subject(s)
Oxygen/chemistry , Porphyrins/chemistry , Titanium/chemistry , Water/chemistry , Adsorption , Calibration , Colloids/chemistry , Hydrogen-Ion Concentration , Models, Chemical , Photochemistry/methods , Photosensitizing Agents/pharmacology , Surface PropertiesABSTRACT
Improved yields for the syntheses of a variety of spiroisoxazolines were achieved through intramolecular cyclization/methylation reactions of functionalized 5,5-disubstituted isoxazolines in one reaction vessel. Aromatic ring containing nitrile oxides and disubstituted geminal alkenes reacted in a 1,3-dipolar fashion to afford the corresponding 5,5-isoxazoline. A comparison of the relative location of the nucleophile and electrophile on the isoxazoline and two different ester functional groups was performed in order to determine the best isoxazoline system for the intramolecular cyclization/methylation reaction.
