Joohoon Kim

Novel optical/electrochemical selective 1,2,3-triazole ring-appended chemosensor for the Al3+ ion

A chemosensor (1) bearing a 1,2,3-triazole ring spacer was synthesized for the selective detection of Al(3+) with respect to dual optical and electrochemical changing events. The addition of Al(3+) ions to 1 induced a significant change in fluorescence intensity, attributable to ICT and CHEF effects from the 1,2,3-triazole ring. The electrochemical behavior of 1 in the presence of the Al(3+) ion was significantly altered compared with those of the other metal cations tested.

Rhodamine-based chemosensing monolayers on glass as a facile fluorescent “turn-on” sensing film for selective detection of Pb2+

Rhodamine-based chemosensors 1 and 2 were synthesized and self-assembled onto glass surfaces for the selective fluorescent sensing of Pb(2+). The immobilized chemosensors showed fluorescent responses that were turned-on with Pb(2+) in CH(3)CN, selectively over various metal ions. The Pb(2+)-selective fluorescent switch of the immobilized chemosensors was also reversible, allowing for repeated use for Pb(2+) detection.

Peptide arrays identify isoform-selective substrates for profiling endogenous lysine deacetylase activity.

This paper reports the development of a class of isoform-selective peptide substrates for measuring endogenous lysine deacetylase (KDAC) activities in cell culture. The peptides were first identified by comparing the substrate specificity profiles of the four KDAC isoforms KDAC2, KDAC3, KDAC8, and sirtuin 1 (SIRT1) on a 361-member hexapeptide array wherein the two C-terminal residues to the acetylated lysine were varied. The arrays were prepared by immobilizing the peptides to a self-assembled monolayer of alkanethiolates on gold and could therefore be analyzed by a mass spectrometry technique termed SAMDI (self-assembled monolayers for matrix assisted laser desorption/ionization time-of-flight mass spectrometry). Arrays presenting the selective substrates were treated with nuclear extracts from HeLa, Jurkat, and smooth muscle cells and analyzed to measure endogenous deacetylase activities. We then use the arrays to profile KDAC activity through the HeLa cell cycle. We find that the activity profile of the KDAC3 selective peptide closely mirrors the changing acetylation state of the H4 histone, suggesting a role for this enzyme in cell cycle regulation. This work is significant because it describes a general route for identifying selective substrates that can be used to understand the differential roles of members of the deacetylase enzyme family in complex biological processes and further because the label-free approach avoids perturbation of enzyme activity that has plagued fluorescence-based assays.

Combining Mass Spectrometry and Peptide Arrays to Profile the Specificities of Histone Deacetylases

This paper introduces the use of mass spectrometry to analyze peptide arrays for applications in profiling enzyme specificity. The strategy is illustrated with arrays containing 361 acetylated peptides to profile the activities of several histone deacetylases (HDACs). The arrays reveal distinct substrates that are preferred by members of the HDAC family. This example is particularly relevant because the label-dependent assays now used for these enzymes constrain the range of substrates that can be assayed and can perturb the intrinsic activities of the enzymes.

The association between some endocrine disruptors and hypospadias in biological samples

Hypospadias is a birth defect found in boys in which the urinary tract opening is not at the tip of the penis. The etiology of hypospadias is still unidentified, but endocrine disruptors are considered as one possible cause of hypospadias. In this study, target endocrine disruptor compounds were established for an assay. The target compounds included 5 phthalates (di-(2-ethylhexyl)phthalate (DEHP), di-n-butyl-phthalate (DBP), mono-(2- ethylhexyl) phthalate (MEHP), mono-n-butyl-phthalate (MBP) and phthalic acid (PA)), 2 alkylphenols (n-nonylphenol (n-NP) and t-octylphenol (t-OP)) and bisphenol A. The association between these 8 endocrine disruptors and hypospadias was studied. The levels of endocrine disruptors in the urine and plasma of a control group were compared with those of a patient group. DEHP (P = 0.006) and n-NP (P = 7.26e-6) in the urine samples and PA (P = 0.009) and BPA (P = 7.22e-10) in the plasma samples showed a significant association with hypospadias. The levels of endocrine disruptors in the urine and plasma of the mothers were also compared to those of the patients to investigate the metastasis of the endocrine disruptors from the mother. These levels did not, however, show a relationship with hypospadias (R2 = 0.001–0.563).

Tunability of the Adsorbate Binding on Bimetallic Alloy Nanoparticles for the Optimization of Catalytic Hydrogenation

In this paper, we show that PtAu and PdAu random alloy dendrimer-encapsulated nanoparticles with an average size of ∼1.6 nm have different catalytic activity trends for allyl alcohol hydrogenation. Specifically, PtAu nanoparticles exhibit a linear increase in activity with increasing Pt content, whereas PdAu dendrimer-encapsulated nanoparticles show a maximum activity at a Pd content of ∼60%. Both experimental and theoretical results suggest that this contrasting behavior is caused by differences in the strength of H binding on the PtAu and PdAu alloy surfaces. The results have significant implications for predicting the catalytic performance of bimetallic nanoparticles on the basis of density functional theory calculations.

Enhanced electrogenerated chemiluminescence of phenylethynylpyrene derivatives: use of weakly electron-donating group as a substituent.

A weakly donating group (n-propyl) has been used as a substituent at the para-position of the phenyl group for a series of phenylethynylpyrene derivatives where the number of phenylethynyl peripheral arms appended to the pyrene core is varied. This system markedly improved the concurrent stability of both cation and anion radicals and consequently greatly improved electrogenerated chemiluminescence (ECL). Density functional theory (DFT)-based theoretical calculations supported the associated photophysical and electrochemical properties of the series compounds.

Decoration of glassy carbon surfaces with dendrimer-encapsulated nanoparticles with a view to constructing bifunctional nanostructures

We demonstrate a method for constructing bifunctional nanostructures, which conjugate biochemical and electrocatalytic activities, on glassy carbon surfaces by decorating the carbon surfaces with both biologically active glucose oxidases and size-monodisperse Pt nanoparticles (less than 2 nm in diameter) utilizing only a single dendrimer layer.

PDMS/MWCNT nanocomposite actuators using silicone functionalized multiwalled carbon nanotubes via nitrene chemistry

We demonstrate that covalently functionalized multiwalled carbon nanotubes (MWCNT) with a silicone copolymer via nitrene chemistry can be used as efficient conductive fillers for silicone dielectric elastomer actuators. The MWCNTs were covalently functionalized with poly(azidopropylmethyl)-co-(dimethylsiloxane) (silicone-N3) bearing an azide group through a nitrene addition reaction. The incorporation of a small amount of the uniformly silicone grafted MWCNTs (silicone-g-MWCNTs) in silicone dielectric elastomer strongly enhanced the mechanical, dielectric, and electromechanical properties of the resulting nanocomposites. This reinforcing effect is attributed to the homogeneous dispersion of silicone-g-MWCNTs in the silicone elastomer matrix due to the large degree of compatibility between the matrix and the passivation layers of the functionalized MWCNT.

Blue luminescence of dendrimer-encapsulated gold nanoclusters.

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl-terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady-state and time-resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au8 and Au13). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.