Chiral three-dimensional supramolecular assemblies: colloidal onions, cubosomes, and hexosomes.

Amphiphilic molecules can self-assemble in solution into a variety of supramolecular assemblies, ranging from simple micelles, ribbons, and tubes to complex cubosomes with bicontinuous cubic nanostructures. It is well known that the self-assembly of chiral building blocks into one-dimensional (1D) twisted fibers, helical ribbons, and tubes enables chiral transfer from the molecular scale to super-assemblies. In this study, we investigate the chirality of three-dimensional (3D) supramolecular assemblies, such as colloidal onions, cubosomes, and hexosomes, formed from the same chiral heteroclusters. Unlike supramolecular 1D helical ribbons, these assemblies do not have chiral external shapes or chiral internal nanostructures, but they do exhibit circular dichroism, suggesting that they are chiral. Structural studies revealed that the ordered arrangement of the chiral units in curved superstructures is the origin of the supramolecular chirality of these 3D assemblies. Therefore, this study provides insights for enriching the diversity and complexity of supramolecular chiral assemblies.

Synthesis of boronate-decorated polyethyleneimine-grafted porous layer open tubular capillaries for enrichment of polyphenols in fruit juices.

A combination between modification with porous layer and grafting of polyethyleneimine (PEI) on the inner face of capillary was for the first time developed for boronate affinity in-tube solid-phase microextraction (SPME) material to enhance the extraction capacity for cis-diol-containing polyphenols. The successful synthesis of boronate-decorated polyethyleneimine-grafted porous layer open tubular (BPPLOT) capillary was confirmed by scanning electron micrograph, Fourier transform-infrared spectra and absorption experiments. The porous layer, PEI and boronate affinity provided high specific surface area, more binding sites for boronate groups and specific selectivity of BPPLOT capillary, respectively. The maximum binding quantity of BPPLOT capillary greatly improved, and ranged from 143 to 170 µg m-1 for cis-diol-containing polyphenols (catechin, chlorogenic acid, caffeic acid and epicatechin). A green method based on boronate affinity in-tube SPME was developed for separation and enrichment polyphenols, and some parameters of in-tube SPME were optimized. After in-tube SPME, HPLC with UV detection was used for quantitative determination of polyphenols. Recoveries of standard spiked cis-diol-containing polyphenols from fruit juice were between 80.9% and 102%, with intra-day and inter-day coefficient of variation ranging from 4.8% to 7.3% and 5.0% to 8.6%, respectively. Conversely, recovery of non-cis-diol-containing ferulic acid was no greater than 3.0%. These results suggested that the BPPLOT capillary could effectively separate and enrich cis-diol-containing polyphenols from real samples.

Ni-Al Bimetallic Catalyzed Enantioselective Cycloaddition of Cyclopropyl Carboxamide with Alkyne.

A Ni-Al bimetallic catalyzed enantioselective cycloaddition reaction of cyclopropyl carboxamides with alkynes has been developed. A series of cyclopentenyl carboxamides were obtained in up to 99% yield and 94% ee. The bifunctional-ligand-enabled bimetallic catalysis proved to be an efficient strategy for the C-C bond cleavage of unreactive cyclopropanes.

Host sensitization of Tb3+ ions in tribarium lanthanide borates Ba3Ln (BO3)3 (Ln = Lu and Gd).

The vacuum-ultraviolet (VUV) spectroscopic properties of undoped and Tb(3+)-doped borates Ba(3)Ln(BO(3))(3) (Ln = Lu and Gd) with different crystal structures were investigated by using synchrotron radiation. Ba(3)Lu(BO(3))(3) (BLB) crystallizes in a hexagonal structure, whereas Ba(3)Gd(BO(3))(3) (BGB) crystallizes in a trigonal structure. The maximum host absorption for BLB and BGB was found to locate at ~179 and ~195 nm, respectively. Upon host excitation, BLB exhibits an intrinsic broad UV emission centered at 339 nm, which is attributed to the recombination of self-trapped excitons that may presumably be associated with band-gap excitations or molecular transitions within the BO(3)(3-) group. In contrast to BLB, no broad emission but line emission ascribed to a Gd(3+)(6)P(J)-(8)S(7/2) transition was observed in the emission spectrum of BGB. Upon doping of Tb(3+) ions into the hosts of BLB and BGB, an efficient energy transfer from the host excitations to Tb(3+) via host/Gd(3+) emission was observed, showing that host sensitization of Tb(3+) occurs in these rare-earth borates.

A novel tunable green- to yellow-emitting ß-YFS:Ce³+ phosphor for solid-state lighting.

A Ce(3+)-activated fluorosulfide phosphor (ß-YFS:Ce(3+)) was synthesized by solid-state reaction in a sealed tube. The crystal structure has been refined from the XRD profiles and there are two different crystallographic rare earth sites, namely, Y(1) and Y(2), where the Ce(3+) ions occupied. The emission band with a maximum at 495 nm of ß-Y(0.99)Ce(0.01)FS phosphor was characterized by the 4f-5d transitions of Ce(3+) ion. With increasing Ce(3+) concentration, the emission variations were observed from 495 to 547 nm. When ß-YFS:Ce(3+) phosphors were utilized to incorporate with n-UV/blue chip, greenish-white light with color rendering index of 65-77 were obtained. The results indicate that the tunable green- to yellow-emitting ß-YFS:Ce(3+) can serve as a potential phosphor for incorporation in fabrication for solid-state lighting. The preparation, spectroscopic characterization, quantum efficiency, thermal-quenching behavior, and related LED device data are also presented.