Cadmium(II) and mercury(II) complexes of an NO2S2-donor macrocycle and its ditopic xylyl-bridged analogue

The NO2S2-donor macrocycle (L1) was synthesised from the ring closure reaction between Boc-N-protected 2,2'-iminobis(ethanethiol) (3) and 2,2'-(ethylenedioxy)bis(benzyl chloride) (4) followed by deprotection of the Boc-group. alpha,alpha'-Dibromo-p-xylene was employed as a dialkylating agent to bridge two L1 to yield the corresponding N-linked product (L2). The X-ray structure of L2 (as its HBr salt) is described. A range of Cd(II) and Hg(II) complexes of L1 (6-9) and L2 (10-12) were prepared and characterised. Reaction of HgX2 (X = Br or I) with L1 afforded [Hg(L1)Br]2[Hg2Br6].2CH2Cl2 6 and [Hg(L1)I(2)] 7, respectively. For 6, the Hg(II) ion in the complex cation has a distorted tetrahedral coordination environment composed of S2N donor atoms from L1 and a bromo ligand. In 7 the coordination geometry is highly distorted tetrahedral, with the macrocycle coordinating in an exodentate manner via one S and one N atom. The remaining two coordination sites are occupied by iodide ions. [Hg(L1)(ClO4)]ClO4 8 was isolated from the reaction of Hg(ClO4)2 and L1. The X-ray structure reveals that all macrocyclic ring donors bind to the central mercury ion in this case, with the latter exhibiting a highly distorted octahedral coordination geometry. The O2S2-donors from the macrocyclic ring define the equatorial plane while the axial positions are occupied by the ring nitrogen as well as by an oxygen from a monodentate perchlorato ion. Reaction of Cd(NO3)(2).4H2O with L1 afforded [Cd(L1)(NO3)2](.)0.5CH2Cl2 9 in which L1 acts as a tridentate ligand, binding exo-fashion via its S2N donors. The remaining coordination positions are filled by two bidentate nitrate ions such that, overall, the cadmium is seven-coordinate. Reactions of HgX2(X = Br or I) with L2 yielded the isostructural 2 : 1 (metal : ligand) complexes, [Hg2(L2)Br4] 10 and [Hg2(L2)I(4)] 11. Each mercury ion has a distorted tetrahedral environment made up of S and N donors from an exodentate L2 and two coordinated halides. Contrasting with this, the reaction of L2 with Cd(NO3)(2).4H2O yielded a 1-D coordination network, {[Cd2(L2)(NO3)4].2CH2Cl2}n 12 in which each ring of L2 is exo-coordinated via two S atoms and one N atom to a cadmium ion which is also bound to one monodentate and one bidentate nitrate anion. The latter also has one of its oxygen atom attached to a neighboring cadmium via a nitroso (mu2-O) bridge such that the overall coordination geometry about each cadmium is seven-coordinate. The [Cd(L2)0.5(NO3)2] units are linked by an inversion to yield the polymeric arrangement.     

Imidazole-based excited-state intramolecular proton-transfer materials: synthesis and amplified spontaneous emission from a large single crystal

We have synthesized a novel class of imidazole-based excited-state intramolecular proton-transfer (ESIPT) materials, i.e., hydroxy-substituted tetraphenylimidazole (HPI) and its derivative HPI-Ac, which formed large single crystals exhibiting intense blue fluorescence and amplified spontaneous emission (ASE). Transparent, clear, and well-defined fluorescent single crystals of HPI-Ac as large as 20 mm x 25 mm x 5 mm were easily grown from its dilute solution. From the X-ray crystallographic analysis and semiempirical molecular orbital calculation, it was deduced that the four phenyl groups substituted into the imidazole ring of HPI and HPI-Ac allowed the crystals free from concentration quenching of fluorescence by limiting the excessive tight-stacking responsible for intermolecular vibrational coupling and relevant nonradiative relaxation. Fluorescence spectral narrowing and efficient ASE were observed in the HPI-Ac single crystal even at low excitation levels attributed to the intrinsic four-level ESIPT photocycle.     

Photocatalytic decomposition of orange II over TiO2-loaded on SBA-15 prepared using a microwave process

SBA-15 mesoporous material was prepared by microwave-hydrothermal method and was used as support in TiO₂-loaded SBA-15 photocatalysts. The physical properties of these particles were investigated. We also examined the activity of these samples as photocatalysts for the decomposition of orange II. Titania loaded on a silica matrix decreases the surface area of the support as expected for TiO₂ incorporation. For TiO₂-loaded SBA-15 photocatalysts, the IR absorption at ∼960 cm⁻¹ commonly accepted as the characteristic vibration of the Ti-O-Si bond. The photocatalytic activity increases with an increase of the TiO₂ loading.     

Characterization and epitope mapping of two monoclonal antibodies against human CD99

CD99 plays a critical role in the diapedesis of monocytes, T cell differentiation, and the transport of MHC molecules. Engagement of CD99 by agonistic monoclonal antibodies has been reported to trigger multifactorial events including T cell activation as well as cell-cell adhesion during hematopoietic cell differentiation. In this study, to identify the functional domains participating in the cellular events, we mapped the epitopes of CD99, which are recognized by two agonistic CD99 monoclonal antibodies, DN16 and YG32. Using recombinant fusion proteins of GST with whole or parts of CD99, we found that both antibodies interact with CD99 molecules independently of sugar moieties. DN16 mAb detected a linear epitope located in the amino terminal region of CD99 while YG32 mAb bound another linear epitope in the center of the extracellular domain. To confirm that the identified epitopes of CD99 are actually recognized by the two mAbs, we showed the presence of physical interaction between the mAbs and the fusion proteins or synthetic peptides containing the corresponding epitopes using surface plasmon resonance analyses. The dissociation constants of DN16 and YG32 mAbs for the antigen were calculated as 1.27 x 10(-7) and 7.08 x 10(-9) M, respectively. These studies will help understand the functional domains and the subsequent signaling mechanism of CD99.     

PIAD — A computer code for peak identification and activity determination

A Peak Identification and Activity Determination (PIAD) computer program has been developed. A new concept of peak significance is introduced and a great change has been made to the currently used associated gamma lines technique in calculating the confidence index; confidence factor is also given to the gamma line of a nuclide that is not seen in the spectrum. The program is written in Fortran IV under the operating system of RSX-11M.     

Heterodimerization of olefins. 1. Hydrovinylation reactions of olefins that are amenable to asymmetric catalysis

Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 degrees C to give 3-(4-bromophenyl)-1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described.     

Status of activation analysis and its applications in Korea

Brief history and current status of activation analysis in Korea are described. About 120 papers have been published since the first paper was reported in 1960. They are sorted out into 5 consecutive periods according to the publication year, and typical feature of each period is described.     

Chiral polymer hosts for circularly polarized electroluminescence devices

Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications. The fabrication of a CP PLED requires a polymer host that provides the appropriate chiral environment around the emitting dopant. However, chemical strategies for the design of chiral polymer hosts remain underdeveloped. We have developed new polymer hosts for CP PLED applications. These polymers were prepared through a free-radical polymerization of 3-vinylcarbazole with a chiral N-alkyl unit. This chiral unit forces the carbazole repeat units to form mutually helical half-sandwich conformers with preferred (P)-helical sense along the polymer main chain. Electronic circular dichroism measurements demonstrate the occurrence of chirality transfer from chiral monomers to achiral monomers during chain growth. The (P)-helical-sense-enriched polymer interacts diastereoselectively with an enantiomeric pair of new phosphorescent (R)- and (S)-dopants. The magnitude of the Kuhn dissymmetry factor (g_abs) for the (P)-helically-enriched polymer film doped with the (R)-dopant was found to be one order of magnitude higher than that of the film doped with the (S)-dopant. Photoluminescence dissymmetry factors (g_PL) of the order of 10⁻³ were recorded for the doped films, but the magnitude of diastereomeric enhancement decreased to that of g_abs. The chiral polymer host permits faster energy transfer to the phosphorescent dopants than the achiral polymer host. Our photophysical and morphological investigations indicate that the acceleration in the chiral polymer host is due to its longer Förster radius and improved compatibility with the dopants. Finally, multilayer CP PLEDs were fabricated and evaluated. Devices based on the chiral polymer host with the (R)- and (S)-dopants exhibit electroluminescence dissymmetry factors (g_EL) of 1.09 × 10⁻⁴ and −1.02 × 10⁻⁴ at a wavelength of 540 nm, respectively. Although challenges remain in the development of polymer hosts for CP PLEDs, our research demonstrates that chiroptical performances can be amplified by using chiral polymer hosts.

Polymer electroluminescence devices producing circularly polarized luminescence (CP PLEDs) have valuable photonic applications.     

Fourier transform infrared spectroscopy study of the effect of pH on anion and cation adsorption onto poly(acrylo‐amidino diethylenediamine)

The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl₃ · 6H₂O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag⁺ > Cu²⁺ > Fe²⁺ > Ni²⁺. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004     

Arsenic trioxide-induced apoptosis is independent of stress-responsive signaling pathways but sensitive to inhibition of inducible nitric oxide synthase in HepG2 cells

Arsenic trioxide (As(2)O(3)) has been found to be remarkably effective in the treatment of patients with acute promyelocytic leukemia (APL). Although evidences for the proapoptotic activity of As(2)O(3) have been suggested in leukemic and other solid cancer cells, the nature of intracellular mechanisms is far from clear. In the present study, we investigated As(2)O(3) affect on the stress-responsive signaling pathways and pretreatment with antioxidants using HepG2 cells. When treated with micromolar concentrations of As(2)O(3), HepG2 cells became highly apoptotic paralleled with activation of caspase-3 and members of mitogen-activated protein kinases (MAPKs) including extracellular signal-regulated kinase (ERK) and c-jun NH(2)-terminal kinase (JNK) but not p38 MAP kinase. However, inhibition of each kinase activity failed to inhibit apoptosis by As(2)O(3). Addition of n-acetyl cysteine (NAC) or diphenyleneiodonium (DPI) effectively protected cells from apoptosis and significantly lowered As(2)O(3)-induced activation of caspase-3. However, neither NAC nor DPI was able to effect ERK or JNK activation induced by As(2)O(3). Guanidinoethyldisulfide dihydrochloride (GED) and 2-ethyl-2-thiopseudourea (ETU), known inhibitors of the inducible nitric oxide synthase (iNOS), also suppressed the apoptotic activity of As(2)O(3). These results suggest that As2O3 induces caspase-mediated apoptosis involving a mechanism generating oxidative stress. However, activation of some stress-responsive signaling pathways by As(2)O(3) may not be the major determinant in the course of apoptotic processes.