Preparation and properties of a selenium-containing catalytic antibody as type I deiodinase mimic

Conversion of thyroxine (T-4) to 3,5,3'-triiodothyronine is an essential first step in controlling thyroid hormone action. Type I deiodinase (DI) can catalyze the conversion to produce the bulk of serum 3,5,3'-triiodothyronine. Acting as a mimic of DI, a selenium-containing catalytic antibody (Se-4C5) prepared by converting the serine residues of monoclonal antibody 4C5 raised against T4 into selenocysteines, can catalyze the deiodination of T4 with dithiothreitol (DTT) as cosubstrate. The mimic enzyme Se-4C5 exhibited a much greater deiodinase activity than model compound ebselen and another selenium-containing antibody Se-Hp4 against GSH. The coupling of selenocysteine with the combining pocket of antibody 4C5 endowed Se-4C5 with enzymatic activity. To probe the catalytic mechanism of the catalytic antibody, detailed kinetic studies were carried out in this paper. Investigations into the deiodinative reaction revealed the relationship between the initial velocity and substrate concentration. The characteristic parallel Dalziel plots demonstrated that Se-4C5-catalyzed reaction mechanism was ping-pong one, involving at least one covalent enzyme intermediate. The kinetic properties of the catalytic antibody were similar to those of DI, with K-m values for T-4 and DTT of approximately 0.8 muM and 1.8 muM, respectively, and a V-m value of 270 pmol per mg of protein per min. The activity could be sensitively inhibited by 6-propyl-2-thiouracil (PTU) with a K-i value of similar to 120 muM at 2.0 muM T-4 concentration. The PTU inhibition was progressively alleviated with the increasing concentration of added DTT, revealing that PTU was a competitive inhibitor for DTT.

Single crystal structure of form I syndiotactic poly(butene-1)

The structures of single crystals of syndiotactic poly(butene-1) in form I, produced by thin-film growth, are studied by transmission electron microscopy and electron diffraction. Bright-field electron microscopy observation shows that the single crystal exhibits a regular rectangular shape with the long axis along its crystallographic b-axis. Electron diffraction results indicate an isochiral C-centered packing of a-fold helical chains in an orthorhombic unit cell corresponding to the C222(1) space group, according to the model proposed in the literature. The differences with the polymorphic behavior of syndiotactic polypropylene concerning the formation and the stability of the isochiral mode of packing are outlined.

Investigation on moleculare and crystal structures of metal complexes with aminopolycarboxylic acids (VII) - Syntheses and structure determination of Na-3[Hg (I) (edta) C1] center dot 6H(2)O

In this paper we describe the moleculare and crystal structures of the Na-3[Hg( II )(edta)Cl] . 6H(2)O (edta=ethylenediamine-N,N,N',N'-tetraacetate). The crystal data are as follows: orthorhombic, a=8. 083 (2) Angstrom , b=13. 870(3) Angstrom , c=38. 617(5) Angstrom , v=4329. 4 (13) Angstrom(3) , Z=8, Dc= 1. 798 g . cm(-3), mu=5. 564 mm(-1), P(000)=2280, R=0. 0317 and R-w=0. 0731 for 3883 unique reflections. In complex, the complex anion [Hg ( II ) (edta)Cl](3-) has a seven-coordination structure like a mono-capped trigonal-prism (C-2v-MTP) in which the edta(4-) acts as a hexadentate ligand with four O atoms and two N atoms and a Cl- caps a quadrilateral face as a seventh ligand. It can be known that the Hg2+ which has a d(10) electronic structure can form a high-coordinate compound with a hexadentate ligand (edta) because it has a big ionic radius.

Synthesis of a photochromic bisphenoxynaphthacenequinone compound by two-step method

A new photochromic bisphenoxynaphthacenequinone compound, 6,6'-[1-methylethylidenebis (4,1-phenyleneoxy)]bis (5,12-naphthacenequinone) (1), was synthesized by a two-step method, i.e., synthesis of 6-[4-(2-(4-hydroxyphenyl)isopropyl) phenoxy]-5, 12-naphthacenequinone (2) from 6-chloro-5, 12-naphthacenequinone (3) and bisphenol-A, and a further reaction of compound 2 in DMF/acetone mixed solvent in the presence of anhydrous potassium carbonate and potassium iodide. The crude product is obtained in a precipitate form and can easily be purified by recrystallization. The solvent composition has marked influence on the yield of the precipitated crude product in the second step.

Isobutane/butene alkylation over supported heteropoly acid catalysts: I. Influence of the structure of silica

Catalysts consisting of heteropoly acids (HPAs) supported on different silica and mesoporous molecular sieves have been prepared by impregnation and the sol-gel method, respectively, and their catalytic behavior in fixed-bed alkylation of isobutane with butene has been investigated. The activity, selectivity and stability of the supported-HPA catalysts could be correlated with the surface acidity of the catalysts, the structure of supports as well as the time on stream (TOS). In the fixed-bed reactor, the acidity of the heteropoly acid is favorable to the formation of dimerization products (C-8(=)); especially, the pore size of supports was seen to have an important effect on activity and product distribution of the catalysts. Contrary to the traditional solid-acid catalysts, the supported-HPA catalysts own an excellent stability for alkylation, which makes it possible for these supported catalysts to replace the liquid-acid catalysts used in industry.

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex - The mimicking for monooxygenase

By [2 + 2] Schiff base condensation of 5 - bromo - 2 - methoxylbenzene - 1,3 - dicarboxaldehyde with diethylenetriamine, a new hexaaza 24 - membered macrocyclic ligand was obtained,which formed a macrocyclic binuclear copper(I) complex in the presence of [Cu . (CH3CN)(4)]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper( II) complex was obtained. The copper( II.) complex was characterized by several methods and its oxidized products was characterized by H-1 NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke; and the phenoxy - and water - bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.

Generation of chiral bis(cyclopentadienyl)neodymium Schiff base complex bearing internal C-C bond formation and hydrogen transfer

NdCl3 reacts with excess CpNa (Cp=Cyclopentadienyl) in THF, followed by sequent treatment with (S)-(+)-N-(1-phenylethyl)salicylideneamine led to the formation of title compound, [GRAPHICS] The X-ray structure determination shows that it is a dimer with internal C-C bond formation and hydrogen transfer between one of Cp ring and the C=N bond of Schiff base ligand. (C) 1997 Elsevier Science S.A.

Synthesis, properties and crystal structure of a heteropoly compound containing titanium

K4H2CoW12O40. 2Ti02 . 9H(2)O crystallizes from an aqueous solution of Na2WO4, Co(OAc)(2) and Ti(SO4)(2). The compound has very similar i.r. and u.v. spectra to those of [CoW12O40](6-) and [CoW11TiO40](8-) but its polarographic behaviour is different from that of [CoW11TiO40](8-) and exhibits only reduction of tungsten(VI). A single crystal structural analysis indicates that this compound consists of the heteropolyanion [CoW12O40](6-), titanium-oxygen chain, potassium ions and water molecules.

ATTEMPTS TO MODIFY AN ELECTRODE WITH A CONDUCTING PLATINUM CLUSTER COMPOUND

A conducting platinum cluster compound K1.64Pt(C2O4)(2) was electrochemically synthesized on a glassy carbon electrode through the electrooxidation of K2Pt(C2O4)(2) in an aqueous medium using single potential step and cyclic voltammetry methods. The precursor K2Pt(C2O4)(2) was prepared by a ligand exchange reaction between C2O42- and PtCl42-. During single potential step experiments, the electrolytic current corresponding to the oxidation of K2Pt(C2O4)(2) increased dramatically after a sharp decrease at the beginning (due to the formation of conducting K1.64Pt(C2O4)(2) on the surface of the working electrode). Two kinds of mechanism account for the current transients at the different applied potentials. Cyclic voltammetry was conducted with K1.64Pt(C2O4)(2) on the surface of the working electrode and a steady-state diffusion current was observed. Since the material grew in a fibrous manner, each conducting fiber which was in contact with the electrode could serve as an ultramicroelectrode. The behavior of the working electrode was thus changed from a plain to an ultramicroelectrode array.

STUDIES ON STRUCTURE OF EO/THF RANDOM COPOLYETHER(I) - NMR-STUDIES ON SOLUTION ACTION AND COMPLEX

The special action of TEO solution was investigated by 1D, 2D-NMR in CDCl3. For the present measurements, when the concentration of TEO was higher in CDCl3, the chemical shift difference (Delta delta) and the peak number of C-13 NMR spectrum were changed with increasing the solution concentration, At lower concentration(< 3% V/V ), the peaks will be closed together for -CH2O- resonance carbon and it is not the appearance of the narrowed, When temperature was changed, the Delta delta value was contrary to the solvent effect, So, the shifts of the resonance carbon in the NMR spectra indicated clearly that the complex formation for the system of CDCl3, and TEO molecular interaction were affected by the experiment temperature and the solution concentration.

STRUCTURE OF AN ERBIUM COORDINATION COMPOUND WITH L-PROLINE, ([ER(PRO)2(H2O)5]CL3)(N)

catena-Poly[{pentaaqua(L-proline-O)-erbium-mu-(L-proline-O:O')} trichloride], {[Er(C5H9-NO2)2(H2O)5]Cl3}n, M(r) = 594.0, monoclinic, P2(1), a = 8.294 (1), b = 10.981 (3), c = 11.934 (3) angstrom, beta = 107.04 (2)degrees, V = 1039.2 (4) angstrom3, Z = 2, D(x) = 1.90 g cm-3, lambda(Mo Kalpha) = 0.71069 angstrom, mu = 45.2 cm-1, F(000) = 586, T = 298 K, R = 0.0244 for 1711 unique reflections [I > 3 sigma(I(o))]. The crystal consists of one-dimensional chains of infinite length in which one L-proline ligand bridges two neighboring Er ions, the other L-proline ligand being monodentate.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR THE LAOXEU3+ (X = CL, BR, I) SERIES

The Angular Overlap Model (AOM) is applied to the LaOX:Eu3+(X = Cl, Br, I) series involving sigma, pi, delta and phi effects based on the experimental energy levels. The calculations are made in two cases. (1) Consider oxygen and halogen having the same bond-length. (2) Consider the real structure. In both cases, the results show that for sigma-bonding parameters, the values of e(sigma) decrease with increasing charge number of halogen, i.e. Cl- > Br- > I-, this indicates that the bonding ability also decreases with this order. The absolute values of each parameter are much larger than zero-therefore they all must be included in a practical analysis. In the second case, the values of the e(pi) parameter are negative, which means a ''back-bonding'' is formed, and this is profitable for the formation of sigma-bonding, usually referred to as ''synergic effect''.

Insulin-like growth factor-binding protein-3 plays an important role in regulating pharyngeal skeleton and inner ear formation and differentiation

Insulin-like growth factor-binding protein (IGFBP)-3 is the major insulin-like growth factor (IGF) carrier protein in the bloodstream. IGFBP-3 prolongs the half-life of circulating IGFs and prevents their potential hypo-glycemic effect. IGFBP-3 is also expressed in many peripheral tissues in fetal and adult stages. In vitro, IGFBP-3 can inhibit or potentiate IGF actions and even possesses IGF-independent activities, suggesting that local IGFBP-3 may also have paracrine/autocrine function(s). The in vivo function of IGFBP-3, however, is unclear. In this study, we elucidate the developmental role of IGFBP-3 using the zebrafish model. IGFBP-3 mRNA expression is first detected in the migrating cranial neural crest cells and subsequently in pharyngeal arches in zebrafish embryos. IGFBP-3 mRNA is also persistently expressed in the developing inner ears. To determine the role of IGFBP-3 in these tissues, we ablated the IGFBP-3 gene product using morpholino-modified antisense oligonucleotides (MOs). The IGFBP-3 knocked down embryos had delayed pharyngeal skeleton morphogenesis and greatly reduced pharyngeal cartilage differentiation. Knockdown of IGFBP-3 also significantly decreased inner ear size and disrupted hair cell differentiation and semicircular canal formation. Furthermore, reintroduction of a MO-resistant form of IGFBP-3 "rescued" the MO-induced defects. These findings suggest that IGFBP-3 plays an important role in regulating pharyngeal cartilage and inner car development and growth in zebrafish.

River mouth bar formation, riverbed aggradation and channel migration in the modern Huanghe (Yellow) River delta, China

This paper addresses the recent (1970s-1990s) processes of river mouth bar formation, riverbed aggradation and distributary migration in the Huanghe River mouth area, in the light of station-based monitoring, field measurements and remote sensing interpretation. The results show that the morphological changes of the river mouth bar have been closely associated with the largely reduced fluvial discharge and sediment load. Landforrn development such as bar progradation occurred in two phases, i.e. before and after 1989, which correspond to faster and lower bar growth rates, respectively. Fast riverbed aggradation in the mouth channel was strongly related to river mouth bar progradation. During 1976-1996, about 2.8% of the total sediment loads were deposited in the river channel on the upper to middle delta. Therefore, the river water level rose by a few meters from 1984 to 1996. The frequent distributary channel migration, which switched the radial channel pattern into the SE-directed pattern in the mid-1980s, was linked with mouth bar formation. Marine conditions also constrain seaward bar progradation. Furthermore, the history of river mouth bar formation reflects human impacts, such as dredging and dyking in order to stabilize the coastal area. (c) 2005 Elsevier B.V. All rights reserved.

Variability in radiocarbon ages of biochemical compound classes of high molecular weight dissolved organic matter in estuaries

High molecular weight dissolved organic matter (HMW-DOM, > 1000 Da) represents a major fraction (> 30%) of dissolved organic carbon (DOC) in the ocean and thus plays an important role in the global biogeochemical cycling of carbon and many other elements. Its organic sources and formation mechanisms, however, are still not well understood especially in estuarine and coastal regions where multiple natural and anthropogenic sources contribute to total HMW-DOM. In this paper we report our measurements of natural radiocarbon (C-14) abundances and stable carbon isotope (C-13) compositions of the major biochemical compound classes: amino acids, carbohydrates and lipids separated from eight HMW-DOM samples collected from five US estuaries as part of our on-going study of sources, distribution and transport of chromophoric dissolved organic matter (CDOM) in estuarine and coastal waters. Distinct differences in both C-14 and C-13 values were found among the bulk HMW-DOM samples as well as the individual compound classes. Radiocarbon ages of the major compound classes varied by as much as 27,000 years in a single sample. The calculated average radiocarbon ages of the compound fractions of HMW-DOM indicate that the total lipid fraction is very "old", while the acid-insoluble fraction is slightly younger. Total amino acid and carbohydrate fractions, however, have relatively modern apparent C-14 ages. The significant variability in C-14 ages among the compound classes indicates not only multiple organic carbon sources but also different formation and turnover pathways controlling the cycling of different biochemical components of HMW-DOM in estuarine and coastal waters. (c) 2006 Elsevier Ltd. All rights reserved.