Shuxin Wang

6-Substituted quinoline-based ratiometric two-photon fluorescent probes for biological Zn2+ detection

New ratiometric two-photon fluorescent probes are developed from 6-substituted quinolines for biological Zn(2+) detection. They show large red shifts and good ratiometric responses upon Zn(2+) binding. They also exhibit high ion selectivities and large two-photon absorption cross sections at nearly 720 nm. Because the new probes are cell-permeable, they can be used to detect intracellular zinc flux under two-photon excitation.

Ligand-exchange synthesis of selenophenolate-capped Au25 nanoclusters

We report the synthesis and characterization of selenophenolate-capped 25-gold-atom nanoclusters via a ligand-exchange approach. In this method, phenylethanethiolate (PhCH(2)CH(2)S) capped Au(25) nanoclusters are utilized as the starting material, which is subject to ligand-exchange with selenophenol (PhSeH). The as-obtained cluster product is confirmed to be selenophenolate-protected Au(25) nanoclusters through characterization by electrospray ionization (ESI) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), thermogravimetric analysis (TGA), elemental analysis (EA), UV-Vis and (1)H/(13)C NMR spectroscopies. The ligand-exchange synthesis of [Au(25)(SePh)(18)](-)[(C(8)H(17))(4)N](+) nanoclusters demonstrates that the core size of gold nanoclusters is retained in the thiolate-to-selenolate exchange process and that the 18 surface thiolate ligands can be completely exchanged by selenophenolate, rather than giving rise to a mixed ligand shell on the cluster. The two types of Au(25)L(18) (L = thiolate or selenolate) nanoclusters also show some differences in stability and optical properties.

A novel quinoline-based two-photon fluorescent probe for detecting Cd2+in vitro and in vivo

A new two-photon fluorescent Cd(2+) probe APQ is developed by introducing a N(1),N(1)-dimethyl-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine binding group and a 4-methoxyphenylvinyl conjugation-enhancing group to the 2- and 6-positions of quinoline. This probe shows a large red shift and good emission enhancement under Cd(2+) binding. It also exhibits a high ion selectivity for Cd(2+) (especially over Zn(2+)) and a large two-photon absorption cross section at 710 nm. Two-photon microscopy imaging studies reveal that the new probe is non-toxic and cell-permeable and can be used to detect intracellular Cd(2+) under two-photon excitation.

A mitochondria-targeted ratiometric two-photon fluorescent probe for biological zinc ions detection

A mitochondria-targeted ratiometric two-photon fluorescent probe (Mito-MPVQ) for biological zinc ions detection was developed based on quinolone platform. Mito-MPVQ showed large red shifts (68 nm) and selective ratiometric signal upon Zn(2+) binding. The ratio of emission intensity (I488 nm/I420 nm) increases dramatically from 0.45 to 3.79 (ca. 8-fold). NMR titration and theoretical calculation confirmed the binding of Mito-MPVQ and Zn(2+). Mito-MPVQ also exhibited large two-photon absorption cross sections (150 GM) at nearly 720 nm and insensitivity to pH within the biologically relevant pH range. Cell imaging indicated that Mito-MPVQ could efficiently located in mitochondria and monitor mitochondrial Zn(2+) under two-photon excitation with low cytotoxicity.

A comparison of the chiral counterion, solvent, and ligand used to induce a chiroptical response from Au25− nanoclusters

A 25-atom gold nanocluster capped with an achiral thiolate exhibits no chiroptical signals in circular dichroism (CD) measurements. Herein, we report a systematic study on the effects of the chiral environment on the CD response from the Au25 metal core. We found that Au25(SC2H4Ph)18(-)TOA(+) dissolved in a chiral solvent did not give rise to a CD response, nor did Au25(SC2H4Ph)18(-) when associated with a chiral counterion (e.g., (-)-N-dodecyl-N-methylephedrinium, DME(+)). Both scenarios imply that the interaction of the chiral counterion (or chiral solvent molecules) with the achiral Au25(SC2H4Ph)18(-) nanocluster is not strong enough to induce CD signals from the metal core. In contrast, when the metal core is capped with chiral ligands (i.e., Au25(SCH2C*H(NH2)CH2Ph)18), strong CD signals in the visible wavelength range were observed. Thus, the induction of CD signals by surface chiral ligands is much stronger than that by the external chiral environment (including the chiral solvent or counterion). This work reveals some further insight into the origin of the chiroptical response of the Au nanoclusters. These chiral nanoclusters hold potential for practical applications in bioconjugation, sensing, and chiral catalysis.

One-pot synthesis of phenylmethanethiolate-protected Au20(SR)16 and Au24(SR)20 nanoclusters and insight into the kinetic control.

We report two synthetic routes for concurrent formation of phenylmethanethiolate (-SCH2Ph)-protected Au20(SR)16 and Au24(SR)24 nanoclusters in one-pot by kinetic control. Unlike the previously reported methods for thiolate-protected gold nanoclusters, which typically involve rapid reduction of the gold precursor by excess NaBH4 and subsequent size focusing into atomically monodisperse clusters of a specific size, the present work reveals some insight into the kinetic control in gold-thiolate cluster synthesis. We demonstrate that the synthesis of -SCH2Ph-protected Au20 and Au24 nanoclusters can be obtained through two different, kinetically controlled methods. Specifically, route 1 employs slow addition of a relatively large amount of NaBH4 under slow stirring of the reaction mixture, while route 2 employs rapid addition of a small amount of NaBH4 under rapid stirring of the reaction mixture. At first glance, these two methods apparently possess quite different reaction kinetics, but interestingly they give rise to exactly the same product (i.e., the coproduction of Au20(SCH2Ph)16 and Au24(SCH2Ph)20 clusters). Our results explicitly demonstrate the complex interplay between the kinetic factors that include the addition speed and amount of NaBH4 solution as well as the stirring speed of the reaction mixture. Such insight is important for devising synthetic routes for different sized nanoclusters. We also compared the photoluminescence and electrochemical properties of PhCH2S-protected Au20 and Au24 nanoclusters with the PhC2H4S-protected counterparts. A surprising 2.5 times photoluminescence enhancement was observed for the PhCH2S-capped nanoclusters when compared to the PhC2H4S-capped analogues, thereby indicating a drastic effect of the ligand that is merely one carbon shorter.