The synthesis and structures of acyclic and macrocyclic thio-, seleno- and telluro-ether complexes of the metallic and metalloid elements of Groups 13-16 reported since 2000 are described. The diverse structures range from discrete monomers through to infinite 1-, 2- or 3-D polymers. The coordination chemistry in this area is quite different to familiar d-block chemistry and the underlying factors are explored. PMID:21706103
Copper(II) complex coordinated with cyclam-type macrocyclic tetramine, C-meso-1,5,8,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane (2Cdmc) has been synthesized and characterized by single crystal X-ray crystallographic analysis and UV?Vis absorption spectra. Solved molecular structure of [Cu(2Cdmc)(H2O)]Cl2?2H2O (1) revealed that macrocyclicligand 2Cdmc was in the most stable trans-III structure, but the C-methyl groups of 2Cdmc adopted energetically unfavorable axial configuration (C-axial). This complex 1 is the second example of complex of cyclam-type tetramine with only axially oriented C-methyl groups. This complex adopted five-coordinated square-pyramidal geometry with one water molecule occupying one of the two apical sites. Network of hydrogen bonds involving counter anions (Cl?...
This review focusses on spin crossover complexes with octahedral metal ions which are bound to a tetraazamacrocyclic ligand and additionally either to two monodentate ligands or to one bidentate ligand. Macrocyclicligands with a sufficiently large ring size prefer to coordinate to metal ions in an equatorial fashion yielding trans-octahedral coordination environments. In contrast, twelve-membered tetraazamacrocycles with high steric rigidity, such as 2,11-diaza[3.3](2,6)pyridinophanes or 2,11-dithia[3.3](2,6)pyridinophane, are prone to form cis-octahedral complexes. While the electronic and the steric properties of the coordinated tetraazamacrocycle in trans-octahedral complexes are very likely responsible for the paucity of observed spin transitions, the cis-octahedral coordination mode ...
Pulse radiolysis was used to examine the nature of the silver species obtained when an aqueous solution containing sequestered Ag"+ ions was reduced by hydrated electrons in the presence of a surfactant macrocyclic crown ether, labeled L, and/or a maltoside surfactant. The initially formed product is the Ag"0(L) species which rapidly loses its ligand (half-life #<=#5 #mu#s) and reacts with another Ag"+(L) ion to form Ag_2"+(L). The latter species decays by a bimolecular process to form the Ag_4"2"+(L)_n species at a faster rate than its ligand free analogue. Ultimately, colloidal metallic silver, (Ag)_n, forms which is stabilized by the surfactant moieties. No long-term stability to the reduced monomolecular species could be obtained.
A series of crown ethers carrying a pyrene group with nitrogen-sulfur donor atoms, that differ in having three, four and five sulfur atoms in the macrocycle was designed and synthesized by the reaction of the corresponding macrocyclic compound and 1-bromomethylpyrene. The influence of metal cations such as Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+ and Al3+ on the spectroscopic properties of the ligands was investigated in acetonitrile-dichloromethane (1:1) by means of absorption and emission spectrometry. Absorption spectra show isosbestic points in the spectrophotometric titration of Fe2+, Zn2+, Cu2+, Pb2+ and Hg2+. The results of spectrophotometric titration experiments disclosed the complexation compositions and complex stability constants of the novel ligands with Fe2+, Zn2+, Cu2+, Pb2+ and Hg2+ cations. The monoazatetrathia crown ether showed good sensitivity for Cu2+ with ...
[3,5-"3H] 4-Azidoclonidine 6 was prepared from [3,5-"3H] 4-aminoclonidine 4 and has emerged as a valuable tool to study the alpha-2-adrenergic receptor. (author)
The use of 2-pyridinealdoxime (paoH)/N,N′-donor ligand (L-L) “blend” in cobalt chemistry has afforded two cationic mononuclear cobalt(III) complexes of the general type [Co(pao)2(L-L)]+,...Full Text Available
Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2'-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. ...
'The objective of this project is to provide a means to optimize ligand architecture for f-block metal recognition. The authors strategy builds on an innovative and successful molecular modeling approach in developing polyether ligand design criteria for the alkali and alkaline earth cations. The hypothesis underlying this proposal is that differences in metal ion binding with multidentate ligands bearing the same number and type of donor groups are primarily attributable to intramolecular steric factors. They propose quantifying these steric factors through the application of molecular mechanics models. The research involves close integration of theoretical and experimental chemistry. The experimental work entails synthesizing novel ligands and experimentally determining structures and binding constants for metal ion complexation by series of ligands in which architecture ...
The synthesis, characterization, and emission properties of a series of Pt(L{sub 2})(S-S) complexes are reported. The (L{sub 2}) ligands include 4,7-diphenyl-1,10-phenanthroline (Ph{sub 2}phen), 4,4{prime}-dimethyl-2,2{prime}-bipyridine (Me{sub 2}bpy), 1,5-cyclo-octadiene (COD), trimethyl phosphite (P(OMe){sub 3}), and the {alpha}-C-deprotonated form of 2-phenylpyridine (2-phpy). The (S-S) ligands include 1-(tert-butoxycarbonyl)-1-cyanoethylene-2,2-dithiolate (tbcda), 1-(diethoxyphosphinyl)-1-cyanoethylene-2,2-dithiolate (cpdt), cis-1,2-dicarbomethoxyethylene-1,2-dithiolate (met), and N,N-diethyldithio-carbamate (Et{sub 2}dtc). The complexes are readily synthesized by the addition of the dithiolate or thiolate ligand to Pt(L{sub 2})Cl{sub 2} except for Pt(P(OMe){sub 3}){sub 2}(met), which is prepared by the addition of 2 equiv of trimethyl phosphite to Pt(COD)(met).
A study was made on complex formation of thiosemicarbazide diacetic acid (H/sub 2/L) with neodymium (3), holmium (3) and erbium (3) in solutions and formation of complexes of metal: ligand=4:1 composition was revealed. Synthesis conditions were developed and products of LnLClxnH/sub 2/O, LnLOHxnH/sub 2/O, Na(LnL/sub 2/)xnH/sub 2/O composition were separated in crystalline state. It was shown, that H/sub 2/L behaves in these compounds as tripod ligand with O, O, N, N donor atoms.
A study was made on complex formation of thiosemicarbazide diacetic acid (H_2L) with neodymium (3), holmium (3) and erbium (3) in solutions and formation of complexes of metal: ligand=4:1 composition was revealed. Synthesis conditions were developed and products of LnLClxnH_2O, LnLOHxnH_2O, Na[LnL_2]xnH_2O composition were separated in crystalline state. It was shown, that H_2L behaves in these compounds as tripod ligand with O, O, N, N donor atoms.
Eu"3"+ and Tb"3"+ complexes with novel branched calix[4]arene ligands incorporating 2,2' -bipyridine subunits functionalized in the 6- or 5,5'-positions have been synthesized and their photophysical properties investigated. High luminescence intensity was obtained for the Eu"3"+ complex of the calix[4]arene ligand carrying four 5,5' -substituted- 2,2' -bipyridines, which has high molar extinction coefficients (#epsilon#_m_a_x 39 600 M"-"1 cm"-"1) and a high luminescence quantum yield (15%). (authors). 12 refs., 2 figs., 1 tab.
2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X2 and [Ni(L)X]X compositions (where L=ligand and X=NO3^-, Cl^- and CH3COO^-) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Oto...
A new bimetallic complex [HNEt3][Cuq2IEu(hfac)3] (q^- = 8-hydroxyquinolinato, hfac^- = hexafluoroacetylacetonate) was prepared simply with only one step and characterized. Upon excitation of the organic ligand q^-, the sensitized europium luminescence was achieved.
One approach in the design of neutral oxotechnetium complexes is based on the simultaneous substitution of a tridentate dianionic ligand and a monodentate monoanionic coligand on a [Tc(V)O]"+"3 precursor. Following this ''mixed ligand'' concept, a novel "9"9"mTc complex with N,N-bis(2-mercaptoethyl)-N'N'-diethylethylenediamine as ligand and 1-octanethiol as coligand is prepared and evaluated as potential brain radiopharmaceutical. Preparation of the complex at tracer level was accomplished by using "9"9"mTc-glucoheptonate as precursor. The substitution was optimized and a coligand/ligand ratio of 5 was selected. Under this conditions the labeling yield was over 80% and a major product (with radiochemical purity > 80%) was isolated by HPLC methods and used for biological evaluation. Chemical characterization at carrier level was developed using the corresponding rhenium complex as structural model. ...
During the past year, further studies on mAChR were conducted. These studies included verification of the difference in pituitary distribution based on ligand charge. The pituitary localization of TRB. A neutral mAChR ligand, was verified. The lack of QNB blockade of TRB uptake was tested by blockage with scopolamine, another mAChR antagonist and by testing the effect in a different strain of rat. Neither scopolamine or change of rat strain had any effect. We concluded that TRB uptake in pituitary is not a receptor-mediated process. Further studies were conducted with an additional quaternized mAChR ligand: MQNB. Pituitary localization of MQNB, like MTRB, could be blocked by pretreatment with QNB. We have tentatively concluded that permanent charge on a mAChR antagonist changes the mechanism of uptake in the pituitary. Time course studies and the effects of DES on myocardial uptake are reported. A brief report on ...
This paper describes the search for new potential chemotherapeutic agents based on transition metal complexes with planar ligands. In this study, palladium polypyridyl complexes were synthesized and characterized by elemental analysis, NMR, UV-VIS and IR spectroscopies. The interaction of the complexes with DNA was also investigated by spectroscopic methods. All metal-to-ligand charge transfer (MLCT) bands of the palladium polypyridyl complexes exhibited hypochromism and red shift in the presence of DNA. The binding constant and viscosity data suggested that the complexes [PdCl{sub 2}(phen)] and [PdCl{sub 2}(phendiamine)] interact with DNA by electrostatic forces. Additionally, these complexes induced an important leishmanistatic effect on L. (L.) mexicana promastigotes at the final concentration of 10 {mu}mol L{sup -1} in 48 h. (author)
The ortho-metalated Pt(II) complexes Pt(ppy)(CO)Cl (1), Pt(ptpy)(CO)Cl (2), and Pt(ppy)(Hppy)Cl (3) (where ppy and ptpy are respectively the ortho-C-deprotonated forms of 2-phenylpyridine and 2-p-tolylpyridine and Hppy is 2-phenylpyridine) have been prepared. The CO ligand is coordinated trans to the nitrogen atom of the ortho-metalated ligand and exerts a strong trans effect resulting in a relatively long Pt-N bond [2.114(19) {angstrom}]. This structure shows both the bidentate ppy ligand and the monodentate Hppy with the nitrogens of these ligands trans to each other. The UV/vis electronic absorption spectra of 1-3 have intense bands in the near-UV region ({approximately}375 nm) which have been assigned as metal to ligand charge transfer (MLCT) transitions, and higher energy bands were assigned as ligand-centered transitions. Each complex exhibits relatively ...
The cyclohexane-1,2-diamine-based bisbinaphthyl macrocycles (S)-/(R)-5 and their cyclic and acyclic analogs are synthesized. The interactions of...Full Text Available
New five complexes of the type of [RuL sub(3-x)(dmby) sub(x)]X sub(2)(x = 1,2,3, L = 2,2'-bipyridyl or 1,10-phenanthroline, dmby = 3,3'-dimethy1-2,2'-bipyridyl, X = halide ion) have been synthesized in order to investigate the effects of two methyl groups of dmby on the absorption and emission spectra, luminescence quantum yields, and lifetimes. Values of the radiative and nonradiative rate constants have been calculated from these data at 77K. Although the absorption and emission maxima and the lifetimes are not much affected by the dmby ligand substitution, the molar extinction coefficients and emission quantum yields are decreased compared with trischelated complexes of the parent bipyridyl or phenanthroline ligands. At 25"0C the emission yields of the complexes containing dmby decrease by 3 - 4 orders of magnitude than at 77K. Possible causes of the decrease in the quantum yields are discussed. (author).
Platinum(II) complexes (1-4) with bidentate N,Nprime-ligands, O,Oprime-dialkyl esters (alkyl = ethyl, n-propyl, n-butyl and n-pentyl), of (S,S)-ethylenediamine-N,Nprime-di-2-(4-methyl)pentanoic acid were synthesized and characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. DFT calculations were performed for the complexes and it was found that only one diastereoisomer could be formed. Cytotoxic activity of complexes 1-4 was determined against chronic lymphocytic leukemia cells (CLL) and compared to the activity of ligand precursors L12HCl-L42HCl and corresponding palladium(II) complexes, [PdCl2L] (L = L1-L4). The complexes were found to exhibit significantly higher antitumor activities than cisplatin on CLL cells. Cytotoxic effect of platinum(II) complexes on CLL cel...
Platinum complexes play an important role in the development of anticancer drugs. Their cytotoxicity can be influenced by the nature of the leaving ligands, due to the hydrolysis reaction that occurs prior to the binding of the platinum complex to DNA. Also, non-leaving groups such as lipophilic diamines may affect cellular uptake. In this work, we describe the synthesis of platinum(II) complexes having oxalato and long chain aliphatic N-alkyl ethylenediamines as ligands. The products were characterized by elemental analyses, infrared spectroscopy and {sup 1}H, {sup 13}C and {sup 195}Pt NMR spectroscopy. Biological activity was assessed against tumor cell lines (A{sub 549}, B16-F1, B16-F10, MDA-MB-231) and non-tumor cell lines (BHK-21 and CHO). The length of the carbon chain affects the cytotoxicity and the oxalato complexes were less cytotoxic than the respective chloride-containing analogues. (author)
Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a...Full Text Available
Conformationally constrained analogue synthesis was undertaken to aid in pharmacophore mapping and 3D-QSAR analysis of nitrobenzylmercaptopurine riboside (NBMPR) congeners as equilibriative nucleoside transporter 1 (ENT1) inhibitors. In our previous study [J. Med. Chem. 2003, 46, 831-837], novel regioisomeric nitro-1,2,3,4-tetrahydroisoquinoline conformationally constrained analogues of NBMPR were synthesized and evaluated as ENT1 ligands. 7-NO2-1,2,3,4-Tetrahydroisoquino-2-yl purine riboside was identified as the analogue with the nitro group in the best orientation at the NBMPR binding site of ENT1. In the present study, further conformational constraining was introduced by synthesizing 5prime-O,8-cyclo derivatives. The flow cytometrically determined binding affinities indicated that the...
A few metal complexes of isatin-isonicotinoylhydrazone with Ni(II), Cr(III), Co(II), Cu(II), Zn(II) and Cd(II) have been prepared and characterized on the basis of elemental analyses, infrared and electronic spectra as well as "1H NMR spectra, conductivity and magnetic measurements. In view of the results obtained, it has been found that two molecules of isatin-isonicotinoylhydrazone are chelated to the central metal ion as bis-uninegative ONO tridentate ligand forming non-electrolytic octahedral metal complexes. (author)
Three novel inosine-based dinuclear platinum complexes have been synthesized via a solid-phase strategy. In these compounds, the metal is linked both to the N-7 of the purine nucleus and to the terminal amine group of a hexylamine side chain installed on N-1. Cis- or trans- diamine as well as ethylenediamine ligands are coordinated to platinum along with a chloride. The synthesised complexes were tested against four different human tumor cell lines. One of these complexes proved to be more cytotoxic than cisplatin against the MCF7 cancer cell line in a short-term exposure assay.
Radioisotopes of Pb(II) have been of some interest in radioimmunotherapy and radioimmunoimaging (RII). However, the absence of a kinetically stable bifunctional chelating agent for Pb(II) has hampered its use for these applications. {sup 203}Pb (T{sub 1/2}=52.02 h) has application potential in RII, with a {gamma}-emission that is ideal for single photon emission computerized tomography, whereas {sup 212}Pb (T{sub 1/2}=10 h) is a source of highly cytotoxic {alpha}-particles via its decay to its {sup 212}Bi (T{sub 1/2}=60 min) daughter. The synthesis of the novel bifunctional chelating agent 2-(4-isothiocyanotobenzyl)-1,4,7,10-tetraaza-1,4,7,10-tetra-(2-carbamoyl methyl)-cyclododecane (4-NCS-Bz-TCMC) is reported herein. The Pb[TCMC]{sup 2+} complex was less labile to metal ion release than Pb[DOTA]{sup 2-} at pH 3.5 and below in isotopic exchange experiments. In addition to increased stability to Pb{sup 2+} ion release at low pH, the bifunctional TCMC ...
Radioisotopes of Pb(II) have been of some interest in radioimmunotherapy and radioimmunoimaging (RII). However, the absence of a kinetically stable bifunctional chelating agent for Pb(II) has hampered its use for these applications. "2"0"3Pb (T_1_/_2=52.02 h) has application potential in RII, with a #gamma#-emission that is ideal for single photon emission computerized tomography, whereas "2"1"2Pb (T_1_/_2=10 h) is a source of highly cytotoxic #alpha#-particles via its decay to its "2"1"2Bi (T_1_/_2=60 min) daughter. The synthesis of the novel bifunctional chelating agent 2-(4-isothiocyanotobenzyl)-1,4,7,10-tetraaza-1,4,7,10-tetra-(2-carbamoyl methyl)-cyclododecane (4-NCS-Bz-TCMC) is reported herein. The Pb[TCMC]"2"+ complex was less labile to metal ion release than Pb[DOTA]"2"- at pH 3.5 and below in isotopic exchange experiments. In addition to increased stability to Pb"2"+ ion release at low pH, the bifunctional TCMC ligand was found to have ...
Varying coordination modes of the Schiff base ligand H"2L [5-methyl-1-H-pyrazole-3-carboxylic acid (1-pyridin-2-yl-ethylidene)-hydrazide] towards different metal centers are reported with the syntheses and characterization of four mononuclear Mn(II), Co(II), Cd(II) and Zn(II) complexes, [Mn(H"2L)(H"2O)"2](ClO"4)"2(MeOH) (1), [Co(H"2L)(NCS)"2] (2), [Cd(H"2L)(H"2O)"2](ClO"4)"2 (3) and [Zn(H"2L)(H"2O)"2](ClO"4)"2 (4), and a binuclear Cu(II) complex, [Cu"2(L)"2](ClO"4)"2 (5). In the complexes 1-4 the neutral ligand serves as a 3N,2O donor where the pyridine ring N, two azomethine N and two carbohydrazine oxygen atoms are coordinatively active, leaving the pyrazole-N atoms inactive. In the case of complex 5, each ligand molecule behaves as a 4N,O donor utilizing the pyridine N, one azomethine N...
Full text: HMPAO, a butane monoxime derivative of propylene amine and ECD, ethyl cysteinate dimer, are currently being used as brain imaging agents. In an effort to develop new radiopharmaceuticals for imaging brain, we have synthesized amine and imine derivatives of ethyl cysteinate with butane monoxime, optimized labelling procedure with "9"9"mTc and studied the in vivo behaviour of their "9"9"mTc complexes. Imine derivative of ethyl cysteinate with butane monoxime was synthesized by refluxing equimolar amounts of butane monoxime and ethyl cystinate in dry benzene for 3 hours. The product was purified over silica with 10% ethyl acetate in chloroform as eluent. Amine derivative was prepared by reducing the imine derivative with sodium borohydride. The ligands were characterized by NMR spectroscopy and were found to be pure. The ligands were labelled with "9"9"mTc using stannous chloride as reducing agent. The complexes were characterized by ...
The symmetrical complexes [{sup 99m}Tc][TcN(R{sub 2}PS{sub 2}){sub 2}] [R = CH{sub 3}, CH{sub 2}CH{sub 3}, CH{sub 2}CH{sub 2}CH{sub 3}, CH{sub 2}(CH{sub 3}){sub 2}], and the unsymmetrical complex [{sup 99m}Tc][TcN(Me{sub 2}PS{sub 2})(Et{sub 2}PS{sub 2})] have been prepared, at tracer level, through a two-step procedure involving the preliminary formation of a prereduced technetium nitrido intermediate followed by substitution reaction onto this species by the appropriate dithiophosphinate ligand [R{sub 2}PS{sub 2}]Na. The chemical identity of the resulting complexes have been established by comparison with the corresponding {sup 99}Tc-analogs prepared, at macroscopic level, by reacting the complex [{sup 99}TcNCl{sub 4}] [n-Bu{sub 4}N] (n-Bu = n-butyl) with an excess of ligand in methanol, and characterized by elemental analyses and spectroscopic techniques. The complexes are neutral and lipophilic, and possess a square pyramidal geometry, with ...
The symmetrical complexes ["9"9"mTc][TcN(R_2PS_2)_2] [R = CH_3, CH_2CH_3, CH_2CH_2CH_3, CH_2(CH_3)_2], and the unsymmetrical complex ["9"9"mTc][TcN(Me_2PS_2)(Et_2PS_2)] have been prepared, at tracer level, through a two-step procedure involving the preliminary formation of a prereduced technetium nitrido intermediate followed by substitution reaction onto this species by the appropriate dithiophosphinate ligand [R_2PS_2]Na. The chemical identity of the resulting complexes have been established by comparison with the corresponding "9"9Tc-analogs prepared, at macroscopic level, by reacting the complex ["9"9TcNCl_4] [n-Bu_4N] (n-Bu = n-butyl) with an excess of ligand in methanol, and characterized by elemental analyses and spectroscopic techniques. The complexes are neutral and lipophilic, and possess a square pyramidal geometry, with an apical Tc N group and two dithiophosphinate ligands spanning the four positions on the ...
The synthesis, characterization of M"vO([CH_3CH_2N(CH_2CH_2S)_2](p-S-Ph-COOCH_2-CH_3)) (M:"9"9"mTc: I, Re: II) is presented in this work, where a pendant ester function is attached to the monothiolate ligand. Chemical structure of I is established after chromatographic comparison with II, synthesized in macroscopic amounts. Complex II is fully characterized by classical methods of analysis showing that the compound adopts a distorted trigonal bipyramidal configuration around the metal. The two sulfur atoms of the tridentate ligand and the oxo group form the basal plane, while the remaining nitrogen atom of the tridentate ligand and the sulfur atom of the monothiolate ligand occupy the apices of the bipyramid. In vitro challenge experiments with glutathione (GSH) in neutral aqueous medium demonstrate, that I suffers nucleophilic attack by GSH and thereby transformation to a more ...
An improved labeling procedure for peptides attached to organometallic 99mTc(III) '4+1' mixed-ligand complexes in which the radiometal is coordinated by a tripodal tetradentate chelator 2,2',2''-nitrilotriethanethiol (NS3) and a monodentate isocyanide ligand is presented. The labeling procedure was evaluated by the synthesis of [99mTc(NS3)(L2-RGD)]. The containing radiopharmaceutically interesting RGD-peptide cyclo[Arg-Gly-Asp-D-Tyr-Lys] was modified with 4-isocyanobutanoic acid (L2) as linker conjugated to N6-Lys to get the monodentate ligand L2-RGD. The structural identity of the 99mTc-conjugate was confirmed by comparison to a Re reference compound. The Tc- and Re-conjugates had matching retention times under identical HPLC conditions. The 99mTc-labeling was performed in a novel one-step procedure using the eluate of a 99Mo/99mTc generator, NS3, the isocyanide modified peptide, SnCl2, Na2EDTA, ...
The Schiff base ligand, 4-isopropylbenzaldehyde[N-(3-oxo-3,4-dihydro-2-quinoxalinyl)hydrazone] (Ipbh), the 1:1 condensation product of 4-isopropylbenzaldehyde and 2-hydroxy-3-hydrazinoquinoxiline, has been synthesized and characterized by X-ray crystallography. A series of complexes of Ipbh with Nickel(II), viz., [Ni(Ipbh)2]Cl2 (1), [Ni(Ipbh)2]Br2 (2), [Ni(Ipbh)2]I2 (3), [Ni(Ipbh)2(CH3OH)2](NO3)2(CH3OH)2 (4) and [Ni(Ipbh)2ClO4]ClO4 (5) have been synthesized. All the complexes were characterized by elemental analysis, molar conductivity, CHN analysis, spectroscopic studies, magnetic susceptibility measurements and TG/DTA methods. The solid-state structure of the complex 4 was established by single crystal X-ray crystallography. In all the complexes, Ipbh acts as a bidentate NO chelating age...
Reaction between [V^I^VO(acac)2] and the ONN donor Schiff base Hpydx-aepy (I) (Hpydx-aepy=Schiff base obtained by the condensation of pyridoxal and 2-aminoethylpyridine) resulted in the formation of a complex [V^I^VO(acac)(pydx-aepy)] (1). Addition of aqueous 30% H2O2 to 1 yields the poor stable oxidoperoxidovanadium(V) complex [V^VO(O2)(pydx-aepy)] (2). Its formation has also been demonstrated in solution by treating 1 with H2O2 in methanol. Reaction of vanadium exchanged zeolite-Y with I in methanol followed by aerial oxidation gave zeolite-Y encapsulated dioxidovanadium(V) complex, abbreviated as [V^VO2(pydx-aepy)]-Y (4). The crystal and molecular structure of 1 has been determined, confirming the ONN binding mode of the ligand. The encapsulated complex [V^VO2(pydx-aepy)]-Y (4) catalyse...
New tetradentate N(2)O(2) donor Schiff bases and their mononuclear Co(II), Ni(II), Cu(II), and Pd(II) complexes were synthesized and characterized extensively by IR, (1)H-, (13)C-NMR, mass, ESR, conductivity measurements, elemental and thermal analysis. Specifically the magnetic and electronic spectral measurements demonstrate the octahedral structures of cobalt(II), nickel(II) complexes and square planar geometries of copper(II), palladium(II) complexes. All the ligands and complexes were screened for their in vitro antibacterial activity against two gram-positive bacteria (Bacillus subtilis, Staphylococcus aureus) and two gram-negative bacteria (Escherichia coli, Klebsiella pneumonia). In this study, Pd(II) complexes exhibited potent antibacterial activity against B. subtilis, S. aureus whereas other metal complexes also exerted good activity towards all tested strains even than standard drugs streptomycin and ampicillin. PMID:21297294
A general approach has been designed to synthesize some mononuclear and binuclear cyclometalated platinum(II) complexes, containing aromatic N-donor ligands with the presence of one Cl- trans to carbon. In this way, cyclometalated platinum(II) complex [Pt(C^N)Cl(dmso)], 1, C^N = N(1),C(2prime)-chelated, deprotonated 2-phenylpyridine and dmso = dimethylsulfoxide, was used as a precursor to react with imidazole derivatives (1-methylimidazole, 2a, imidazole, 2b,), monodentate pyridine derivatives (4-methylpyridine, 2c, pyridine, 2d,) and bidentate pyridine derivative (4,4prime-bipyridine, 3 and 4,). Synthesized complexes were fully characterized by using multinuclear NMR spectroscopy (1H, 13C{1H} and 195Pt), correlation NMR spectroscopy (1H-1H COSY, 13C{1H}-1H Heteronuclear Multiple Quantum C...
Novel complexes of the type (Pt(DACH)(N-R-iminodiacetate)), wherein DACH represents (R,S)- and (R,R)-1,2 diaminocyclohexane and R represents /minus/Me, /minus/EtOH, and /minus/CH/sub 2/Ph groups, have been prepared, purified, and characterized by spectroscopic techniques (/sup 1/H, /sup 13/C, and /sup 195/Pt NMR;MS(FAB);IR) and by the measurement of selected physical properties (pH, pK/sub a/, conductivity, and molecular weights). The data are consistent with the formation of two diastereomeric complexes in unequal proportions in which the N-R-iminodiacetate ligand appears to be bonded as a pseudofacial tridentate chelate. One are of the ligand forms a stable five-membered-ring O,N-chelate while the other arm appears to be involved in ion-pair formation (zwitterion-like) involving the carboxylate anion and the formally positive Pt(II) central metal atom. It has been demonstrated indirectly that an active impurity was present in predictably ...
Targeted studies completed include the evaluation of tritiated N-0437, evaluation of "3"5S-cysteamine, evaluation of "1"8F-FDG and initiation of synthetic efforts towards the synthesis of iodinated N-0437 and pergolide analogs. The direction of the project has been changed due to several factors which include the decided lack of favorable experimental results, the excellence of results using muscarinic receptor ligands in pituitary, brain and heart and the contention of the DOE review panel that the original grant proposal was based on flawed assumptions together with their perceived lack of importance to pituitary imaging. In the final year of this grant, three studies will be completed. The first study is the continuation of synthetic efforts to prepare iodinated N-0437 and pergolide analogs for possible use as brain imaging agents. The second study is directed towards completion of biochemical evaluation of various muscarinic receptor ...
Targeted studies completed include the evaluation of tritiated N-0437, evaluation of /sup 35/S-cysteamine, evaluation of /sup 18/F-FDG and initiation of synthetic efforts towards the synthesis of iodinated N-0437 and pergolide analogs. The direction of the project has been changed due to several factors which include the decided lack of favorable experimental results, the excellence of results using muscarinic receptor ligands in pituitary, brain and heart and the contention of the DOE review panel that the original grant proposal was based on flawed assumptions together with their perceived lack of importance to pituitary imaging. In the final year of this grant, three studies will be completed. The first study is the continuation of synthetic efforts to prepare iodinated N-0437 and pergolide analogs for possible use as brain imaging agents. The second study is directed towards completion of biochemical evaluation of various muscarinic ...
Some acylhydrazine derived ONO donor Schiff bases and their Co(II) and Ni(II) complexes have been prepared having the same metal ion (cation) but different anions. These synthesized metal(II) complexes have been characterized on the basis of their elemental analyses, magnetic moment, molar conductance, and IR and electronic spectral data. All of the Schiff base ligands function as tridentates and the deprotonated enolic form is preferred for coordination. In order to evaluate the effect of anions on the bactericidal activity, these synthesized complexes, in comparison to the uncomplexed Schiff bases have been screened against bacterial species., Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa and the results are reported. PMID:18475936
Two peptide ligands conjugated adenine, [9-N-(tritylmercapto acetyl diglycyl aminoethyl) adenine, Tr-MAG_2-Ade] and [9-N-(tritylmercapto acetyl triglycyl aminoethyl) adenine, Tr-MAG3-Ade], are synthesized and labeled with "9"9"mTc by directly labeling method. The stability of "9"9"mTc-MAG_2- adenine and "9"9"mTc-MAG_3-adenine in vitro is measured. The uptake radios of tumor to muscle at 3h post-injection are 5.70 and 4.92, respectively. The biodistribution and scintigraphic imaging studies show that the two complexes have high localization in tumor and high contrasted tumor images can be obtained, which suggest their potential utility as tumor imaging agents. But the high radioactivity of abdomen could prevent the tumor imaging in this area. (author)
We have obtained convincing evidence for localization of the optical electron on a single-ring fragment of a chelated bipyridine-like'' ligand (ie., pyridylpyrazine or 4-Methyl-bipyridine). In addition we have completed studies of Ru(bipyrazine){sub 3}{sup 2+} in aqueous sulfuric acid (0--98% by weight) and find clear evidence for sequential addition of six-protons to the six peripheral nitrogen atoms. Studies of zeolite-entrapped complexes are continuing and a series of homo- and heteroleptic complexes have been prepared and characterized. Finally, the synthesis of zeolite-entrapped metallophthalocyanines has now been developed and the copper and cobalt analogues synthesized. The characterization of these materials is now in progress.
Reactions of At(#THETA#)"+, 'At"0.H_2O', AtCl_2"- and AtBr_2 with the pseudohalogenides tricyanomethanide and azide are described. Information on the compound formation of astatine with C(CN)_3"- and N_3"- could be obtained on the basis of electromigration investigations under variation of the conditions (composition of the electrolyte, pH, exchange reactions of ligands). Astatine(I)-tricyanomethanide is classified between AtI_2"- and At(SCN)_2"-. The formation of astatine(I)-azide-compounds is confirmed. Their composition is probably At(N_3)_2"-. There is no dependence of the ion mobility of astatine(I)-azide in the investigated range on azide concentration which is due to its high stability. (author).
Research conducted since the last progress report includes the synthesis and characterization of twenty three novel proton-ionizable crown ether compounds. Metal ion complexation behavior of new and previously-synthesized proton-ionizable crown ether compounds has been probed by solvent extraction and transport across polymer-supported liquid membranes. The behavior of neutral polyether and proton-ionizable polyether ligands in polymeric membrane electrodes has been assessed. Studies of the use of proton-ionizable crown ethers for separation of lithium isotopes were initiated. Also, the thermodynamics of interactions between alkali metal cations and ionized crown ethers have been probed by titration calorimetry. 10 refs., 1 tab.
Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)-trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of ''free amines''. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake studies show increases in ...
Silanization of the silica gel surface in the synthesis of silica gel polyamine composites uses (chloropropyl)-trichlorosilane (CPTCS). It is possible to substitute a molar fraction of reagent CPTCS with methyltrichlorosilane (MTCS), creating a mixed silane surface layer. Two types of silica gels were modified with a series of MTCS:CPTCS molar ratios. Solid-state CP/MAS 29Si and 13C NMR spectroscopies were used to evaluate the surface silane composition. Surface silane coverage was markedly improved for the resulting gels. When polyamines were grafted to the resultant MTCS:CPTCS silane layers, it was shown that the decrease in the number of propyl attachments to the polyamine resulted in increased quantities of ''free amines''. Optimum MTCS:CPTCS ratios were determined for three polyamines grafted onto one silica gel. A substantial free amine increase was observed for poly(allylamine) (PAA). Metal uptake studies show increases in ...
We report the synthesis of four diorganotin(IV) compounds of Schiff base pyruvic acid hydrazone derivatives formulated as [R2SnLY]2, where L1 is 2-SC4H3CON2C(CH3)CO2 with Y = CH3CH2CH2CH2OH, R = n-Bu (1); L2 is C6H5CON2C(CH3)CO2 with Y = CH3CH2OH, R = p-F-Bz (2); L3 is 2-HOC6H4CON2C(CH3)CO2 with YH2O, R = p-CN-Bz (3); and L4 is 4-NO2-C6H4CON2C(CH3)CO2 with YCH3CH2OH, R = Bz (4). The structures of all compounds have been established by a combination of single-crystal X-ray diffraction analysis, 1H and 119Sn NMR spectroscopy, IR spectroscopy, and elemental analysis. Studies reveal that four ligands present the same coordination mode with tin center, which all present tridentate ONO donor Schiff bases and coordinate to the tin center in an enolic form. In compounds 1-4, each tin atom is seven...
BackgroundThe epidermal growth factor receptor (Egfr) with its numerous ligands has fundamental roles in development, cell differentiation and physiology. Dysfunction of the receptor-ligand...Full Text Available
One- and two-dimensional NMR techniques have been used to investigate the solution structures of (2S,6S,11S,15S)-2,6,11,15-tetramethyl-1,4,7,10,13,16-hexaoxacyclooctadecane (I) and (2R,3R,11R,12R)-2,3,11,12-tetramethyl-1,4,7,10,13,16-hexaoxyacyclooctadecane (II) macrocycle complexes of CaCl{sub 2} and Ca(NO{sub 3}){sub 2} in CDCl{sub 3}. Previous chiroptical studies of these and similar crown complexes by circularly polarized luminescence (CPL), total luminescence (TL), and circular dichroism (CD) spectroscopy have shown that the macrocycle asymmetric carbons in these complexes constrain the ring such that the sense of the ring twist in the S chiral ring complexes is opposite to that in the R chiral ring complexes. These studies have also shown that there is an added chirality element in the di- and trivalent (alkaline earth and lanthanide metal, respectively) nitrate complexes of I and II associated with the twist of the nitrate anions ...
Control of human filarial infections currently depends on chemotherapeutic strategies predominantly directed at microfilariae. Doxycycline therapy in an extended daily dose regimen sterilizes and kills adult stages, but the utility of this drug for routine field use remains an issue of concern. No macrofilaricidal drugs with efficacy after one or two doses are available for use, delaying the achievement of the elimination or eradication of onchocerciasis and lymphatic filariasis. Moxidectin, a macrocyclic lactone, is currently in clinical trials for onchocerciasis. A few other drugs that have already been approved for use in veterinary practice or in human medicine for other indications are available for investigation. Early drug discovery pipelines are poorly populated and the process of ...
Bis(diphenylphosphino)phenylamine can be selectivity oxidized by S or Se in toluene or hexane solvents to the monooxidized thioyl or selenoyl products Ph[sub 2]PN(PH)PPh[sub 2]=E, (E = S, Se). These compounds act as bidentate chelate ligands toward metal complexes forming (CO)[sub 4]M(LL) (M = Mo, W), CO(Cl)Rh(LL), and Cl[sub 2]M(LL), (M = Pt, Pd) where (LL) is the thioyl or selenoyl derivative of the aminobis(phosphine). IR and NMR data are given for all complexes. The carbonyl infrared stretching frequencies show that the chelates form with the phosphine cis to any CO which is present. The [sup 31]P NMR of all complexes of two doublets except for the Rh complexes wherein the Rh spin also couples to phosphorous to produce two doublets of doublets. The [sup 2]J[sub PP] values range from 56 to 112 Hz. [sup 1]J[sub PSe] coupling provide valuable assistance for the assignment of the phosphorus resonances which range widely from 55 to 126 ppm for P[sup III] and from 60 ...
A series of (diamine)isopropylidenmalonatoplatinum(II) complexes and the oxidation products, (diamine)Pt(OOC){sub 2}C=C(CH{sub 3}){sub 2}(X){sub 2}, (diamine=ethylenediamine(en), 1,2-diaminopropan(dap), N-methylethylenediamine(men); X=OH, OCOCH{sub 3}, OCOCF{sub 3}), have been prepared, and their interaction with guanosine-5'-monophosphate (5'-GMP) have been examined by means of {sup 1}H NMR spectroscopy. The present platinum(II) complexes have shown to interact with 5'-GMP through N7 coordination in two consecutive steps in a similar way as with cisplatin, but no interaction between the present platinum(IV) complexes and 5'-GMP was observed. However, in the presence of ascorbic acid, the platinum(IV) complexes have been found to interest with 5'-GMP with the reation rate depending on their reduction rate.
NMR and CD studies indicate that Mg/sup 2 +/ and Ca/sup 2 +/ are able to change the conformation of tetracycline in DMSO solution. This may affect the in vivo effect of tetracycline. Using /sup 23/Na NMR, the formation constant of NaLAS (LAS represents the anion of lasalocid A) was found to be 80 M/sup -1/ which is much smaller than that in less polar solvents. Spin-lattice relaxation measurements were made to study the binding sites of Gd/sup 3 +/ on Las in ChCl/sub 3/-DMF mixed solvent system. No intermediate conformation (between cyclic and open-chain) was found. LAS was found to be a good second-sphere ligand to inert transition-metal amines. NMR studies suggest that LAS is in cyclic conformation when bound to these metal amines. A new method for the synthesis of spin-labeled anticancer Pt(II) complexes was developed. It is very simple and gives high yield of pure spin-labeled Pt(II) complexes.
A new hydroxyiminoamide ligand, 1-(2-nitroimidazole-1-yl)-propanhydroxyiminoamide (N2IPA) was synthesized. The biodistribution of {sup 99m}Tc-N2IPA in mice bearing S180 tumor demonstrated that the complex showed a selective accumulation in tumor and slow clearance from it. The tumor-to-tissue uptake ratios increased with time. At 4 hours after injection, the uptake ratios of tumor to muscle, blood, liver, heart, and lung reached 8.4, 1.5, 0.6, 2.9, and 2.3, respectively. Moreover, the tumor-to-liver uptake ratio steadily increased to 0.9 at 8 hours and 2.3 at 24 hours. The complex showed little uptake and quick clearance in blood, lung and other organs. Compared with other proposed hypoxia-imaging agents, this novel agent has advantages of higher tumor-to-muscle and tumor-to-blood uptake ratios and easier synthesis.
New palladium(II) and platinum(II) complexes of saccharinate (sac), trans-[Pd(py)"2(sac)"2] (1), cis-[Pt(py)"2(sac)"2] (2), trans-[Pd(3-acpy)"2(sac)"2] (3) and cis-[Pt(3-acpy)"2(sac)"2] (4) (py=pyridine and 3-acpy=3-acetylpyridine) have been synthesized. Elemental analysis, UV-Vis, IR, NMR and TG/DTA characterizations have been carried out. The structures of 1-4 were determined by X-ray diffraction. The palladium(II) and platinum(II) ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of py or 3-acpy, forming a distorted square-planar geometry. The palladium(II) complexes (1 and 3) are trans isomers, while the platinum(II) complexes (2 and 4) are cis isomers. The mononuclear species in the solid state are connected by weak intermolecular C-H...O hydrogen bonds, C-H...@...
A series of new non-discoid chiral copper(ii)-salen type complexes, [Cu((4-CnH2n+1O)2salen)], n = 14, 16, 18 and salen = N,N'-cyclohexane bis (salicylideneiminato), containing 4-substituted alkoxy tails in the side aromatic rings and a cyclohexane spacer, have been prepared and their mesogenic properties investigated. The compounds were characterised by Fourier transform infra-red spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy, UV-vis spectroscopy and fast atom bombardment mass spectrometry. Mesomorphic properties of these compounds were studied by polarising optical microscopy, differential scanning calorimetry and X-ray diffraction (XRD). The ligands are non-mesogenic but the complexes exhibited enantiotropic rectangular columnar mesophases (Colr) with extended temperat...
The dodecanuclear rhenium anionic complex with terminal hydroxo ligands [Re12CS17(OH)6]6? was obtained by the reaction of K6[Re12CS17(CN)6]?20H2O with molten KOH at 300 ?C. The cluster complex was crystallized as a potassium salt from aqueous solution. The reaction between K6[Re12CS17(OH)6]?4H2O and Na2S2O4 in water under reflux results in the formation of the complex Na12[Re12CS17(SO3)6]?48.5H2O. Both new compounds were characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The electronic structure of [Re12CS17(OH)6]6? was also elucidated by DFT calculation
Crystalline bis(O,O'-di-sec-butyldithiophosphato)platinum(II) was prepared and studied by means of 13C, 31P CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the platinum(II) compound is comprised of one centrosymmetric mononuclear molecule [Pt{S2P(O-sec-C4H9)2}2], in which the dithiophosphate groups display structural equivalence in both 31P NMR and XRD data. A pair of the dithiophosphate ligands exhibit the same S,S'-bidentate chelating structural function and form two planar four-membered chelate rings, [PtS2P], in this molecule. The planar configuration of the [PtS4] chromophore in structure 1 is governed by the dsp2-hybrid state of platinum(II). The structural states of the dithiophosphate groups in two different samples of complex 1 (one crystallised from...
In the course of observing by means of Auger spectroscopy graphite gasification reactions catalyzed by metals, it has been found that in the presence of hydrogen, nickel appears to diffuse from the surface into the bulk of the graphite. When potassium is deposited on graphite, it is volatilized above 400/sup 0/C. Surprisingly the production of methane and carbon dioxide from the reaction of graphite and steam was catalyzed by potassium at as low a temperature as 250/sup 0/C. It has been shown that literature on the alkylation of benzene with synthesis gas is erroneous and that the products reported are due to Lewis acid catalyzed cracking of benzene. A novel cobalt mediated, reversible cleavage of a vinyl-hydrogen bond has been discovered. All products from the thermal decomposition of tetralin have been identified. The stereochemistry of cis-1, 2 dihydrotetralin was determined. In the utilization of the water gas shift reaction as a reducing agent for model coal ...
Magnetic coupling between two or more metal centers is an important facet of d- and f-block transition metal chemistry due to its implications in chemical bonding. With respect to actinide metals, magnetic coupling between polymetallic actinide centers is less well-known. Of the few documented examples, only one bimetallic uranium(V) complex, [(MeC{sub 5}H{sub 4}){sub 2}U]{sub 2}[{mu}-1,4-N{sub 2}C{sub 6}H{sub 4}] (1), has unequivocally demonstrated antiferromagnetic coupling. This complex employs a {pi}-conjugated 1,4-phenylenedimide ligand system which bridges the two f{sup 1}-metal centers and enables antiferromagentic coupling between unpaired f-e1ectrons residing in a {pi}-symmetry orbital. In this communication, we report the synthesis of a dimeric bis(imido) uranium(V) iodide complex and demonstrate with magnetic susceptibility measurements and density functional theory (DFT) calculations that the f{sup 1}-uranium centers display ...
Paper describes a new procedure to synthesize a pharmaceutical containing "2"1"1At. "2"1"1At"- anion was found to bind strongly with Rh"3"+ cation complexing with a thio-ether ligand - 1,5,9,13-tetratiacyclohexadecane-3,11-diol (16-S4-diol). One made use of "1"3"1I isotope to seek for the optimal conditions of the reaction. The derived complexes were studied by means of the paper electrophoresis, the ion exchange, the surface chromatography. One studied the kinetics of "1"3"1I"- anion binding with Rh(16-S4-diol), the dependence of the yield of "1"3"1I-Rh(16-S4-diol) forming complex on the temperature. the acidity of the reaction mixture and the concentration of the reagents. On the basis of the determined conditions of the synthesis one prepared "2"1"1At-Rh(16-S4-diol) complex by more astatide ("2"1"1At"-) to the equivalent amounts of RhCl_3 and tetra-thio-ether (16-S4-diol). One studied its behaviour
New platinum(II) complexes with asymmetrically substituted chiral diamine ligands A{sub 2}PtX{sub 2}, (A{sub 2}=NH{sub 2}CH(CH{sub 3})CH{sub 2}NH(c-C{sub 5}H{sub 9}) (apcpa), NH{sub 2}CH(CH{sub 3})CH{sub 2}NH(c-C{sub 6}H{sub 11}) (apcha); X{sub 2}=2Cl, isopropylidenmalonate (IPM), 1,1'-cyclobutandicarboxylate (CBDCA) have been synthesized and characterized by means of elemental analyses, infrared and NMR spectroscopies, and X-ray crystallography. The crystal structures of (S-apcha)Pt[CBDCA]{center_dot}3H{sub 2}O (orthorhombic, P2{sub 1}2{sub 1}2(No. 18), a=6.926(3), b=15.243(3), c=19.319(4) A, V=2039.5(10) A{sup 3}, Z=4, R=0.072) and (S-apcha)Pt[IPM]{center_dot}2.5H{sub 2}O (monoclinic, P2/c(No. 13), a=9.882(1), b=18.502(1), c=22.056(1) A, V=4032.8(5) A{sup 3}, Z=8, R=0.093) exhibit that the platinum atoms achieve a typical square planar arrangement with two nitrogen atoms in cis position and with the chiral center retained. The spectroscopic data disclose ...
Three regio-isomers of N-(N-benzylpiperidin-4-yl)-4-iodobenzamide, IBP, were prepared and evaluated for their sigma affinities. All three isomers (2, 3, and 4-substituted) showed high affinities for sigma-1 receptors in guinea pig brain membranes (Ki - 1.64 nM, 3.02 nM, 1.70 nM respectively) against ["3H]-(+)-pentazocine, a sigma-1 selective ligand. 2-IBP and 4-IBP showed modest affinities for sigma-2 sites in rat liver (Ki = 29.6 nM. 25.2 nM respectively) against ["3H]DTG in the presence of dextrallorphan to mask sigma-1 sites. The homologous competition binding studies of 4-["1"2"5I]BP in MCF-7 human breast tumor cells showed high affinity dose-dependent binding. Competition binding studies with haloperidol and DTG also showed a high affinity binding (Ki = 4.6 nM, 60 nM respectively), demonstrating the sigma specificity. The saturation binding (Scatchard analysis) of ["3H]DTG with MCF-7 cell membrane preparations gave Kd of 24.54 nM and a Bmax of 2071 fmol/mg ...
A burgeoning interest in technetium coordination chemistry has been spurred by its widespread use in nuclear medicine. Recent focus has been on the design and preparation of new technetium complexes, the lipophilicity, polarity, and overall charge of which can be readily altered by simple substitutions in the molecular framework of the ligand in order to optimize the biodistribution and target specific organs. Examples are cationic (Cardiolite) and neutral (Ceretec) technetium complexes, used as myocardial and brain imaging agents, respectively. The authors have been pursuing a continuing study of tris(3-hydroxy-4-pyridinonato)gallium and -indium complexes that are water soluble, are hydrolytically stable, and are of varying lipophilicity and neutral charge. Studies of in vivo in rabbits and mice have revealed that several of these cationic complexes may be useful as morphologic kidney imaging agents, with [{sup 99m}Tc(pap){sub 3}]{sup +} showing elevated levels in ...
A burgeoning interest in technetium coordination chemistry has been spurred by its widespread use in nuclear medicine. Recent focus has been on the design and preparation of new technetium complexes, the lipophilicity, polarity, and overall charge of which can be readily altered by simple substitutions in the molecular framework of the ligand in order to optimize the biodistribution and target specific organs. Examples are cationic (Cardiolite) and neutral (Ceretec) technetium complexes, used as myocardial and brain imaging agents, respectively. The authors have been pursuing a continuing study of tris(3-hydroxy-4-pyridinonato)gallium and -indium complexes that are water soluble, are hydrolytically stable, and are of varying lipophilicity and neutral charge. Studies of in vivo in rabbits and mice have revealed that several of these cationic complexes may be useful as morphologic kidney imaging agents, with ["9"9"mTc(pap)_3]"+ showing elevated levels in the kidneys ...
Six uranyl coordination compounds, UO_2(OH)(PYCA) (1), UO_2(PYCA)_2(H_2O).2H_2O (2), UO_2(PIC)_2 (3), UO_2(H_2O)_2(NIC)_2 (4), UO_2(OH)(HINIC)(INIC) (5), and UO_2(PYTAC)_2(H_2O)_2 (6) were grown as single crystals via hydrothermal synthesis (PYCA - pyrazine-2-carboxylate, PIC - picolinate, NIC - nicotinate, INIC - iso-nicotinate, and PYTAC - 2-(pyridin-4-yl)thiazole-5-carboxylate) to study their optical properties. All six compounds have been identified via single crystal X-ray diffraction and fully characterized via powder X-ray diffraction, infrared spectroscopy, UV-Vis spectroscopy, and fluorescence spectroscopy. Three of the complexes, 1, 3, and 6, represent new structures, and their synthesis and structural characterization is detailed within. The structures of 2, 4, and 5 have previously been reported in the literature. Coordination polymer 1 crystallizes in the orthorhombic space group Pca21 (a = 13.5476(5) Angstroms, b = 6.6047(2) ...
Serotonin is one of the neurotransmitters found in the brain and mediates brain functions. It is very well known that serotonin related brain abnormalities are exerted mainly via serotonin receptors in a similar manner to other neurotransmitters found in the brain. Recently, it has also been found that serotonin is involved in Alzheimer's disease either directly or indirectly by its actions on serotonergic neurons. To understand and treat the diseases caused by abnormalities in the serotonergic system in the brain, it is certain that its mechanism of function has to be well investigated. So far several 5-HT receptors and receptor subtypes have been well characterized. Moreover, serotonin agonists and antagonists acting on specific receptors are chemically synthesized and are now available for the prevention or treatment of serotonergic related diseases. In recent years, a great demand for developing neuroimaging agents has emerged for the diagnosis of abnormal brain functions in the ...
An aliphatic thiol ligand of CuInS2/ZnS core/shell quantum dots is replaced with a hydroxyl-terminated thiol ligand by utilizing `on-off state' of ligands during growth stage of the quantum dots. After the ligand-exchange, negligible differences were observed on both photoluminescence spectrum and luminescent quantum efficiency. The reason for the high retention of luminescent efficiency comes from no local agglomeration and no surface deterioration of QDs. It is also observed that 70% of initial ligands are exchanged by the replacing ligand, determined by FT-IR and 1H NMR. The proposed method provides the quantum dots with an excellent dispersibility in polar solvents, supported by identical luminescence decay characteristics of the QDs.
Studies of various established human bladder and renal carcinoma cell lines cultured in vitro demonstrated the presence of specific, saturable, high affinity binding sites for /sup 125/I-labeled human interferon Beta ser IFN-beta ser). This recombinant produced interferon labeled with approximately one atom of /sup 125/I/molecule of IFN expressed minimal or no loss of antiviral activity. A single class of binding sites (1000-2000/cell) with an affinity constant of 10(10)-10(11) L/M was measured at 4 degrees C for cells exhibiting widely different sensitivity to the antiproliferative effect of IFN-beta ser. Major fluctuations in the binding of /sup 125/I-labeled IFN-beta ser to cellular receptors were observed during in vitro proliferation of four of five cell lines examined. A significant decrease (P less than 0.001) in specific binding was observed 48 h after cultures were established. Cell cycle analysis suggested that within the first 24 h and in the very late log and stationary ...
Rhenium is technetium`s third row congener and exhibits many of the chemical properties that technetium displays. Theoretically, a Re-PhAT complex will be isostructural with the {sup 99m}Tc PhAT complexes that have been prepared for use as brain imaging agents. A series of neutral rhenium(V) oxo complexes was synthesized by the reaction of ReOBr{sub 4}{sup {minus}} with diamino-thiol-thioether ligands of the type (RSC(CH{sub 3}){sub 2})CH{sub 2}NH(o-C{sub 6}H{sub 4})NHCH{sub 2}C(CH{sub 3}){sub 2}SH. The complexes were characterized by IR, UV/visible, and {sup 1}H and {sup 13}C NMR spectroscopy and by fast-atom-bombardment mass spectroscopy. The single-crystal X-ray structure determination on two of the complexes, where R = CH{sub 2}CH{double_bond}CH{sub 2} and CH{sub 2}CH{sub 2}-CH{sub 3}, showed them to consist of a square pyramidal Re{sup V}ON{sub 2}S{sub 2} core. ReO[CH{sub 2}{double_bond}CHCH{sub 2}SC(CH{sub 3}){sub 2}CH{sub 2}N(o-C{sub 6}H{sub 4})NCH{sub ...
The stereocontrolled total synthesis of 4-hydroxydictyolactone (4), a member of the xenicane diterpene family of natural products, is described. These studies feature the development...Full Text Available
The effect of low concentrations of nalidixic acid on ribonucleic acid (RNA) synthesis in Escherichia coli was examined. It was observed that RNA synthesis in exponentially growing...Full Text Available
The parathyroid hormone receptor (PTHR) is a class B G protein-coupled receptor that plays critical roles in bone and mineral ion metabolism. Ligand binding to the PTHR involves interactions to both...Full Text Available
OBJECTIVEThis randomized, four-arm, placebo-controlled, dose-ranging phase 2 trial was conducted to determine whether repeated subcutaneous injections of the altered peptide ligand,...Full Text Available
TCDD and other polyhalogenated aromatic hydrocarbon ligands of the aryl hydrocarbon receptor (AHR) have been classically considered as non-genotoxic compounds because they fail to be directly mutagenic...Full Text Available
Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes...Full Text Available
We studied a novel universal spectrochemical series of six-coordinated octahedral 3d transition metal complexes, which can be used for any combination of central metal atom and ligand molecules. A two dimensional spectrochemical series could be used to estimate the ligand field splitting energy of not only known compounds but also the unknown compounds. Therefore, it should be possible to control the physical properties, such as the electronic and magnetic properties and the optical phenomena of octahedral transition metal complexes by modifying the ligand field splitting. PMID:19378561
The thermodynamics of protonation and europium(III) complex formation with substituted methane diphosphonic acids have been reported recently. These ligands form strong complexes with europium in moderately acidic solutions ((H{sup +}) {ge} 0.1 M), conditions not conducive to complexation by most carboxylate and aminopolycarboxylate ligands. A correlation of log {beta} vs pK{sub a} values for phosphonate and carboxylate ligands is used to explore the effect of ligand structure on complex stability. 5 refs., 1 fig.
Peroxisome proliferator activated receptor-{gamma} (PPAR{gamma}) regulates metabolic homeostasis and adipocyte differentiation, and it is activated by oxidized and nitrated fatty acids. Here we report the crystal structure of the PPAR{gamma} ligand binding domain bound to nitrated linoleic acid, a potent endogenous ligand of PPAR{gamma}. Structural and functional studies of receptor-ligand interactions reveal the molecular basis of PPAR{gamma} discrimination of various naturally occurring fatty acid derivatives.
Although polybrominated naphthalenes (PBNs) are contaminants of the commercial fire retardant fireMaster BP-6, the individual PBN isomers have not been identified. In order to study PBNs possessing an analogous level of bromination to those found in fireMaster BP-6, three synthetic PBN mixtures, averaging 5.0, 5.3, and 5.6 bromines per naphthalene were synthetized and partially characterized. The PBN mixtures were administered to immature male Wistar rats and found to be potent inducers of cytochrome P-450-dependent monooxygenases. At the lowest dose tested, 30 mumol X kg-1, each PBN mixture caused maximal induction of benzo(a)pyrene hydroxylase activity. On the basis of enzyme activities, ligand-binding spectra and sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the PBN mixtures were determined to be 3-methylcholanthrene-type inducers of cytochrome P-450 (P-448), resembling qualitatively the most toxic polyhalogenated biphenyls, dibenzofurans, and ...
The hydration behavior of a number of square planar Pt(II) bis(cyano) complexes has been examined, and the limiting stoichiometries are related to the steric requirements of the dinitrogen bidentate ligands coordinated to the metal center. In particular, the IR, UV/vis, and [sup 1]H, [sup 13]C, and [sup 195]Pt NMR spectroscopic data for the compound Pt[sup II]dtbipy(CN)[sub 2] [dtbipy = 4,4[prime]-[l brace]C(CH[sub 3])[sub 3][r brace][sub 2]-2,2[prime]-bpy] have been determined and show that, at relative humidities (rh) above [approximately]40%, this complex sorbs five water molecules at room temperature. The sorption process consists of a rapid step in which one H[sub 2]O adds to the complex and which appears to be independent of rh, followed by a slower, rh-dependent step leading to the final stoichiometry. In contrast, the analogous 2,2[prime]-bpy complex sorbs no water under these conditions, while the 4,4[prime]-(CH[sub 3])[sub 2]-2,2[prime]-bpy complex sorbs ...
We describe the synthesis and characterization of superparamagnetic iron oxide nanoparticle based heavy metal sorbents with various surface chemistries that demonstrate an excellent affinity for the separation of heavy metals in contaminated water systems (i.e. spiked Columbia river water). The magnetic nanoparticle sorbents are prepared from an easy to synthesize iron oxide precursor, followed by a simple, one-step ligand exchange technique to introduce the organic surface functionality of interest chosen to target either specific or broader classes of heavy metals. Functionalized superparamagnetic nanoparticles are excellent sorbent materials for the extraction of heavy metal contaminants from environmental and clinical samples since they are easily removed from the media once bound to the contaminant by simply applying a magnetic field. These engineered magnetic nanoparticle sorbents have an inherently high active surface area (often > ...
We describe the synthesis of metal-chelating polymers (MCPs) with four different pendant polyaminocarboxylate ligands (EDTA, DTPA, TTHA, DOTA) and an orthogonal end-group, either a fluorescein molecule or a bismaleimide linker for antibody attachment. Polymer characterization by a combination of (1)H NMR, UV/vis absorption measurements, and thermal gravimetric analysis (TGA) indicated that each chain of the fluorescein-terminated polymers contained one dye molecule. These polymer samples were loaded with three different types of lanthanide ions as well as palladium and platinum ions. The numbers of metal atoms per chain were determined by a combination of UV/vis and conventional ICP-MS measurements. The experiments with lanthanide ions demonstrated that a net anionic charge on the polymer is important for water solubility. These experiments also showed that at least one type of lanthanide ion (La(3+)) is capable of forming a bimetallic complex ...
Scandium reacts with 4-(2-pyridylazo)resorcinol in the presence of monocarboxylic acids (X) to form mixed-ligand complexes with a Sc:PAR:x ratio of 1:2:2. The chemical nature of this interaction has been established, and the extraction of these mixed-ligand complexes has also been investigated; stability constants and molar extinction coefficients have been calculated. The values of the latter decrease in the order CH_3COOH > CH_2ClCOOH > CCl_3COOH. The formation and extraction of mixed-ligand complexes in Sc-PAR-HX systems make it possible to increase the sensitivity and selectivity of scandium determination in comparison with the use of the Sc-PAR mono-ligand complex.
A study was made of the kinetics of L-(/sup 3/H)quinuclidinyl benzilate binding with membrane-bound muscarine cholinoreceptors from the rat brain. Determination was made of the rate constants of this process, and constants as a function of ligand concentration was investigated, indicating that there is a complex mechanism of interaction of antagonists with muscarine receptor. With up to 3.5 nM concentrations of L-(/sup 3/H)quinuclidinyl benzilate, the binding reaction occurs in two stages: rapid equilibrated binding is followed by a slow process of conformational isomerization of the receptor-ligand complex. At higher ligand concentrations, there is additional drastic increase in constant of rate of ligand binding a new plateau is reached. Such dependence of rate constant on ligand concentration is indicative of the cooperative nature of interaction between antagonists and muscarine ...
Three abiotic systems are described that catalyze the reductive dehalogenation of heavily halogenated environmental pollutants, including carbon tetrachloride, trichloroethene, and perchloroethene. These systems include (a) an electrolytic reactor in which the potential on the working electrode (cathode) is fixed by using a potentiostat, (b) a light-driven system consisting of a semiconductor and (covalently attached) macrocycle that can accept light transmitted via an optical fiber, and a light-driven, two-solvent (isopropanol/acetone) system that promotes dehalogenation reactions via an unknown mechanism. Each is capable of accelerating reductive dehalogenation reactions to very high rates under laboratory conditions. Typically, millimolar concentrations of aqueous-phase targets can be dehalogenated in minutes to hours. The description of each system includes the elements of reaction mechanism (to the extent known), typical kinetic data, and a discussion of the ...
A series of oxine ligands, 5-X, 8 OH C9H6N (X = H, Cl, SO3H) have been covalently bound to a silica gel polyamine composite made from a silanized amorphous silica xerogel and poly(allylamine) (BP-1) by the Mannich reaction. The resulting modified composites WP-4(X = H), CB-1(X = Cl), and SB-1(X = SO3H) were characterized by elemental analysis, FTIR, and solid state CPMAS-13C-NMR. Using the analytical data before and after the ligand modification, the ligand loading could be estimated and in combination with metal ion capacities a metal to ligand ratio could be obtained. The composites WP-4 and CB-1 both showed ratios of approximately 1 : 1 while the sulfonate modified composite, SB-1, showed a metal to ligand ratio of 1 : 2. This is tentatively interpreted in terms of a zwitterionic oxine ...
In order to increase the sensitivity of photometric determination of tungsten and to find forms with high molar extinction coefficients, mixed-ligand complexes of tungsten with antipyrine and trihydroxyfluorone have been studied. The molar extinction coefficients have been determined for chloride associates of mixed-ligand complexes containing different trioxyfluorones: phenylfluorone, salicylflourone, p-bromphenylfluorone, anthrafluorone, dioxyfluorescein, and dioxyfluoroscein ethylate (DOFE). An associate formed by DOFE has the maximum molar extinction coefficient. It has been used for photometric determination of microgram amounts of tungsten impurity in vanadyl sulphate.
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10{sup -5} to 10{sup -3} M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br{sup -} and I{sup -}. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
Reaction of At(I) with triphenylphosphine, triethylphosphite and tri-n-octylphosphine oxide was investigated in ethanolic solution by means of electromigration. A cationic complex with triphenylphosphine was identified being stable at pH = 1,9 in the concentration range of the ligand between c = 10"-"5 to 10"-"3 M. At a higher ligand concentration and at pH>2, the reduction effect of phosphine is superimposed on the complex formation. Complex formation is confirmed by ligand exchange reactions with Br"- and I"-. A comparatively weak complex is formed by triethylphosphite and At(I). No compound is formed by tri-n-octylphosphine oxide and At(I). (orig.).
Three photaffinity labeled derivatives of epothilone D were prepared by total synthesis, using efficient novel asymmetric synthesis methods for the preparation of two important synthetic building...Full Text Available
Bisaminoethanethiol (BAT) ligands with various gem-dimethyl and amide groups were prepared, and the corresponding neutral Tc-99m complexes were prepared and evaluated for their relative stabilities by ligand-exchange reactions. It was demonstrated that technetium complexes containing gem-dimethyl substituents have higher lipophilicities, whereas those with an amide group possess greater stability, which enhances ligand-exchange reaction. The most interesting observation was that the brain uptake in rats is not determined only by lipophilicity. Apparently, Tc-99m complexes with an amide functional group display lower brain uptakes in rats compared to those without an amide group. The brain uptake was strongly influenced by substituents on the BAT ligand. These factors are critically important and should be taken into consideration when designing Tc-99m-labeled agents for CNS receptor imaging.
Abstract Copper(II) bis(thiosemicarbazone) are very useful for blood flow and hypoxic imaging. The aim of this study was to identify structure-activity relationships (SARs) within a series of analogues with different substitution patterns in the ligands, in order to design improved hypoxia imaging agents and elucidate hypoxia selectivity mechanisms. Genetic algorithms (GAs) were used to develop specific copper metal-ligand force field parameters for the MM3 force-field calculations. These new parameters produced results in good agreement with experiment and previously reported copper metal-ligand parameters. A successful quantitative SAR (QSAR) for predicting the several classes of Cu(II)-chelating ligands was built using a training set of 21 Cu(II) complexes. The QSAR exhibited a correlat...
Orphan G protein-coupled receptors (GPCRs) are receptors lacking endogenous ligands. Found by molecular biological analyses, they became the roots of reverse pharmacology, in which receptors are attempted...Full Text Available
The availability of dimeric Pt(I) complexes with bridging bis(diphenylphosphino)methane ligands, (L--L')/sup n+/, presents an opportunity to study the physical properties and reactivity of metal-metal bonds as a function of the ligand trans to it with a minimum of competing variables. Several interesting trends of Pt-P coupling constants with the Pt-L and Pt-Pt bond lengths in Pt(I) dimers, (L--L')/sup n+/, and structurally related Pt(II) complexes are reported here. The data indicate that the Pt-P coupling constants continue to be sensitive indicators of not only the structure and stereochemistry of platinum phosphine complexes but also the electronic and steric influences of the ligand in such complexes, 23 references, 1 figure, 4 tables.
Carbohydrate-directed endocytosis is mediated by a receptor, the hepatic binding protein; it is responsible for the clearance of galactose-terminated glycoproteins from the circulation. This process...Full Text Available
Many microbial pathogens recognize oligosaccharides displayed on the surface of host cells as receptors for toxins and adhesins. These ligand-receptor interactions are critical for disease pathogenesis,...Full Text Available
Single crystals of RbBaTaS{sub 4} (1) and K{sub 2}BaTa{sub 2}S{sub 11} (2) were obtained from the reactions of Ta, with in situ formed fluxes of A{sub 2}S{sub 3} (A = K, Rb), BaS, and S at 500 C. Compound 1 crystallizes in the orthorhombic space group Pnma with a = 9.3286(5), b = 7.0391(4), c = 12.4365(7) A, V = 816.6(1) A{sup 3}, Z = 4. Compound 2 crystallizes in the monoclinic space group P2{sub 1}/c with a = 14.5280(10), b = 12.6347(7), c = 17.5148(12) A, {beta} = 94.744(8) , V = 3203.9(4) A{sup 3}, Z = 4. The structure of RbBaTaS{sub 4} (1) consists of isolated tetrahedral [TaS{sub 4}]{sup 3-} anions and Rb{sup +} and Ba{sup 2+} cations. The Ba{sup 2+} cations are surrounded by nine sulfur atoms forming distorted tricapped trigonal prisms, whereas the Rb{sup +} cations are in an irregular environment of ten sulfur atoms. The structure of K{sub 2}BaTa{sub 2}S{sub 11} (2) consists of two different dinuclear [Ta{sub 2}S{sub 11}] units which are separated by Ba{sup 2+} and K{sup +} ...
The aim of this work is to understand the reasons for the selectivity shown in the complexation by unsaturated heteropolyanions (HPA) of actinides (An) which are oxidized to the number +IV. Different studies have been carried out, both in solution and in solid state, on P_2W_1_7O_6_1"1"0"- and its complexes with Zn"2"+, UO_2"2"+, Ce"4"+, Th"4"+ and U"4"+ to characterize the nature of the complexation site offered to the cation. Among the actinides(IV), the U"4"+ ion has been selected due to its singular spectroscopic and magnetic properties. An initial series of studies, in solution, using NMR"3"1P has thus enabled us to characterize these complexes and to compare them to those formed with the complexing agent PW_1_1O_3_9"8"-. This body of data allows to identify an identical complexation site for both ligands. An analysis of the NMR"3"1P spectrum of U(P_2W_1_7O_6_1)_2"1"6"- has shown a plane of symmetry passing through the actinide and enables us to confirm the ...
Robert A. Martock. Cleveland State University, Cleveland, Ohio. Synthesis and Structural Characterization of a. Novel Indium Mercapto Derivative. [Clln(SCH. 2 ...
A new method of the synthesis of high molecular polybutylene terephthalate (PBT) is developed with the use of Irganox 1010, tris(nonylphenyl) phosphite and hypophosphite as stabilizers and boron nitride or boron oxide as a catalyst is proposed.
Consideration is given to results of investigation into thorium complexing with morin (H_2Mor) in extraction systems containing different carboxylic acids as well as different salt background. The obtained data enabled to suggest the method of photometric determination of thorium in the form of Th(HMor)_2Benz_2 different-ligand complex (where Benz-anion of benzilic acid) with 0.25 #mu#g/ml detection limit.
Using the PMR method the interaction of zirconium and hafnium tetrachlorides with tri.tet.butylphenyl ester of 1,2- naphthoquinonediazide (2)-5-sulfonic acid is studied. The formation of MCl/sub 4/xNQD complexes is established, the equilibrium constants and thermodynamic parameters of complexing reaction are determined. The presence of rapid ligand exchange, proceeding according to associative mechanism, is detected. The rate constants and activation energies of the exchange reaction are calculated.
Using the PMR method the interaction of zirconium and hafnium tetrachlorides with tri.tet.butylphenyl ester of 1,2- naphthoquinonediazide (2)-5-sulfonic acid is studied. The formation of MCl_4xNQD complexes is established, the equilibrium constants and thermodynamic parameters of complexing reaction are determined. The presence of rapid ligand exchange, proceeding according to associative mechanism, is detected. The rate constants and activation energies of the exchange reaction are calculated.
Titanium and aluminum alkoxide derivatives with polymerizable ligands such as 2-(methacryloyloxy)ethylacetoacetate (HAAEMA), oleic acid and geraniol (HOGE) have been obtained. The various compounds have been characterized by FT-IR and NMR {sup 1}H. Copolymerization with styrene and divinylbenzene affords porous doped organic materials which have been characterized by scanning electron microscopy (SEM), elemental analysis, density measurements.
Occupational and environmental exposure to organic ligands, solvents, fuel hydrocarbons, and polychlorinated biphenyls are linked with increased risk of hematologic malignancies. DOE facilities and waste sites in the U.S. are contaminated with mixtures of potentially hazardous chemicals such as metals, organic ligands, solvents, fuel hydrocarbons, polychlorinated biphenyls and radioactive isotopes. A major goal of this project was to establish linkage between chemical/radiation exposure and induction of genomic damage in target populations with the capability to undergo transformation.
We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO4), sulphate (SO4), selenate (SeO4) and selenite (SeO3)] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO4~SO43 PO4. The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO4 whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline e...
The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.
In APCs, presentation by MHC II molecules of the chemically dominant peptide from the protein hen egg white lysozyme (HEL) generates different conformational isomers of the peptide-MHC II complexes (pMHC). Type B pMHCs are formed in early endosomes from exogenous peptides in the absence of H2-DM, whereas in contrast, type A pMHC complexes are formed from HEL protein in late vesicles after editing by H2-DM. Thus, H2-DM edits off the more unstable pMHC complexes, which are not presented from HEL. In this study, we show that type B pMHC complexes were presented from HEL protein only after stimulation of dendritic cells (DC) with TLR ligands or type I IFN. Type I IFN contributed to most TLR ligand-induced type B pMHC generation, as presentation decreased in DC lacking the receptor for type I IFNs (IFNAR1(-/-)). In contrast, presentation of type A pMHC from HEL and from peptide was minimally affected by TLR ligands. The relative ...
Asialoorosomucoid (ASOR) is internalized and degraded by HepG2 cells after binding to the asialoglycoprotein (ASGP) receptor, internalization through the coated pit/coated vesicle pathway, and trafficking to lysosomes. Primaquine, an 8-aminoquinoline antimalarial compound, inhibits ASOR degradation at concentrations greater than 0.2 mM by neutralizing intracellular acid compartments. This leads to alterations in surface receptor number, receptor-ligand dissociation, and receptor recycling. We have investigated the effects of primaquine on 125I-ASOR uptake and degradation as a function of primaquine concentration and duration of exposure. Concentrations below those required for neutralization of acidic compartments block 125I-ASOR degradation in HepG2 cells and lead to intracellular ligand accumulation. This effect is maximal at 80 microM primaquine. The intracellular 125I-ASOR is undegraded, dissociated from the ASGP receptor, and contained ...
Asialoorosomucoid (ASOR) is internalized and degraded by HepG2 cells after binding to the asialoglycoprotein (ASGP) receptor, internalization through the coated pit/coated vesicle pathway, and trafficking to lysosomes. Primaquine, an 8-aminoquinoline antimalarial compound, inhibits ASOR degradation at concentrations greater than 0.2 mM by neutralizing intracellular acid compartments. This leads to alterations in surface receptor number, receptor-ligand dissociation, and receptor recycling. We have investigated the effects of primaquine on 125I-ASOR uptake and degradation as a function of primaquine concentration and duration of exposure. Concentrations below those required for neutralization of acidic compartments block 125I-ASOR degradation in HepG2 cells and lead to intracellular ligand accumulation. This effect is maximal at 80 microM primaquine. The intracellular 125I-ASOR is undegraded, dissociated from the ASGP receptor, and contained ...
Unlike the well-characterized nuclear function of the Notch intracellular domain, it has been difficult to identify a nuclear role for the ligands of Notch. Here we provide evidence for the nuclear function of the Notch ligand Delta-like 1 in colon cancer (CC) cells exposed to butyrate. We demonstrate that the intracellular domain of Delta-like 1 (Dll1icd) augments the activity of Wnt signaling-dependent reporters and that of the promoter of the connective tissue growth factor (CTGF) gene. Data suggest that Dll1icd upregulates CTGF promoter activity through both direct and indirect mechanisms. The direct mechanism is supported by co-immunoprecipitation of endogenous Smad2/3 proteins and Dll1 and by chromatin immunoprecipitation analyses that revealed the occupancy of Dll1icd on CTGF promot...
Subcellular-fractionation techniques were used to characterize the endocytic pathway followed by ricin in rat liver in vivo and tentatively identify the site(s) at which the ricin interchain disulphide...Full Text Available
BackgroundThe aryl hydrocarbon receptor (AhR) is a ligand-activated transcription factor that mediates the toxicity and biological activity of dioxins and related chemicals. The...Full Text Available
CBP and its paralog p300 are histone acetyl transferases that regulate gene expression by interacting with multiple transcription factors via specialized domains. The structure...Full Text Available
Potassium dichlorido(l-prolinato)platinate(II), K[PtCl"2(l-pro"?"H)] (1), and chlorido(dimethyl sulfoxide)(l-prolinato)platinum(II), [PtCl(l-pro"?"H)(dmso)] (2), were synthesized by ligand substitution reactions. Both complexes were characterized by ^1H, ^1^3C, and ^1^9^5Pt NMR spectroscopy, elemental analysis, and HR-ESI-MS. The molecular structures of 1 and 2 were determined by single crystal X-ray diffraction, proving bidentate coordinated l-prolinato ligand and SP-4-4 configuration of 2a. With the help of DFT calculations stability of possible isomers of 1 and 2 was studied. A considerable difference in the in vitro cytotoxicity of 1 versus 2a (exchange of one chlorido ligand by dmso) against four human cancer cell lines was found.
The second messenger signaling molecule bis-(3′-5′)-cyclic dimeric guanosine monophosphate (c-di-GMP) regulates many processes in bacteria, including motility, pathogenesis,...Full Text Available
The effects of selected ligands on the structure of the truncated heavy-chain chemomechanical motor domains of Drosophila ncd and human kinesin were compared using the technique of transient electric...Full Text Available
Bisaminoethanethiol (BAT) ligands with various gem-dimethyl and amide groups were prepared, and the corresponding neutral Tc-99m complexes were prepared and evaluated for their relative stabilities by ligand-exchange reactions. It was demonstrated that technetium complexes containing gem-dimethyl substituents have higher lipophilicities, whereas those with an amide group possess greater stability, which enhances ligand-exchange reaction. The most interesting observation was that the brain uptake in rats is not determined only by lipophilicity. Apparently, Tc-99m complexes with an amide functional group display lower brain uptakes in rats compared to those without an amide group. The brain uptake was strongly influenced by substituents on the BAT ligand. These factors are critically important and should be taken into consideration when designing Tc-99m-labeled agents for CNS receptor imaging.
Receptor activator of NF-kB ligand (RANKL) and osteoprotegerin (OPG) play key roles in the pathogenesis of glucocorticoid-induced osteoporosis (GIO). The aim of our study was to determine whether the...Full Text Available
Binding of epidermal growth factor (EGF) to the EGF receptor (EGFR) initiates signal transduction, ultimately leading to altered gene expression. Ligand-activated EGFR is also rapidly internalized...Full Text Available
Genetic algorithms (GA) were used to develop specific copper metal-ligand force field parameters for the MM3 force field, from a combination of crystallographic structures and ab initio...Full Text Available
A cholinesterase was partially purified from bush bean (Phaseolus vulgaris L.) roots by using acridinium-based ligand affinity chromatography. The procedure gave a 78-fold increase in specific activity,...Full Text Available
Host cells use metabolic signaling through the LXRα nuclear receptor to defend against Listeria monocytogenes infection. 25-Hydroxycholesterol is a natural ligand of LXRs that...Full Text Available
The aim of this study was to assess the utility of a radioimmunoconjugate containing a lead radionuclide for therapy and scintigraphy applications. The radioimmunoconjugate evaluated consisted of a bifunctional DOTA ligand and monoclonal antibody (MAb) B72.3 using athymic mice bearing LS-174T tumors, human colon carcinoma xenografts. In the studies reported here, the lead-203-DOTA complex itself was first demonstrated to have in vivo stability. MAb B72.3 was then conjugated with the DOTA ligand and labeled with "2"0"3Pb, and the immunoreactivity of B72.3 was maintained. The localization of the radioimmunoconjugate to tumor tissue and other select organs paralleled that of DOTA-"1"2"5I-B72.3, suggesting a similar metabolic pattern of the two radioimmunoconjugates. Thus, the DOTA-metal complex does not alter the behavior of the radioimmunoconjugate. Tumor localization of the "2"0"3Pb-DOTA-B72.3 conjugate was demonstrated with biodistribution ...
Osteoblasts are the primary cells responsible for bone formation. They also support osteoclast formation from bone marrow precursors in response to osteotropic factors by inducing receptor activator...Full Text Available
The programming of cellular networks to achieve new biological functions depends on the development of genetic tools that link the presence of a molecular signal to gene-regulatory activity. Recently,...Full Text Available
The aryl hydrocarbon receptor (AHR) is a ligand-activated transcription factor that mediates the toxicity of 2,3,7,8-tetrachlorodibenzo-p-dioxin. However, the role of the AHR...Full Text Available
BackgroundOne virulence property of Borrelia burgdorferi is its resistance to innate immunity, in particular to complement-mediated killing. Serum-resistant B....Full Text Available
AIM: To investigate the relation of Fas and Fas ligand (FasL) protein expression with carcinogenesis and metastasis of gastric carcinoma.METHODS: Immunohistochemistry was used to detect Fas and...Full Text Available
The binding interactions of four ligands differing in acid-base properties with human serum albumin (HSA) were examined as a function of temperature. Binding to HSA decreased with increasing temperature...Full Text Available
Cd36 is a small-molecular-weight integral membrane protein expressed in a diverse, but select, range of cell types. It has an equally diverse range of ligands and physiological functions, which has...Full Text Available
The CD1 family of proteins binds self and foreign glycolipids for presentation to CD1-restricted T cells. To identify previously uncharacterized active CD1 ligands, especially those of microbial origin,...Full Text Available
Bacterial pathogens use virulence strategies to invade epithelial barriers, but active processes of epithelial cells may also contribute to the endocytosis of microbial particles. To focus on the latter,...Full Text Available
BackgroundMolecular docking methods are commonly used for predicting binding modes and energies of ligands to proteins. For accurate complex geometry and binding energy estimation,...Full Text Available
Albumin is a multifunctional transport protein that binds a wide variety of endogenous substances and drugs. Insulins with affinity for albumin were engineered by acylation of the epsilon-amino group...Full Text Available
Peroxisome proliferator-activated receptors (PPARs) are ligand-activated transcription factors belonging to the nuclear hormone receptor superfamily. Their discovery in the 1990s provided insights...Full Text Available
Gamma interferon (IFN-γ) and the cellular responses induced by it are essential for controlling mycobacterial infections. Most patients bearing an IFN-γ receptor ligand-binding chain...Full Text Available
Six kinds of diamino-dithiol compounds are labelled with "9"9Tc"m by ligands exchange reaction. Their ligands exchange percentage is over 95%. The biodistribution of one of these compounds in mice shows 0.88% brain uptake after two minutes and 0.28% after 15 minutes respectively. Although the brain uptake is lower for this compound, it has longer retention in brain. So, the experiment results are valuable to the design of new brain imaging agent in the future.
The first preparation and characterization of the platinum (II) complexes containing five phosphorus ligands are reported herein. The complexes are represented by the formulae (Pt(PP/sub 3/)(P(OR)/sub 3/)Cl/sub 2/, where R = Me or Et, and (Pt(PP/sub 3/)(PEt/sub 3/))Cl/sub 2/. The /sup 31/P spectra of the complexes are presented. 10 references, 2 tables.
Of the radionuclides with physical properties most suited for use with monoclonal antibody for tumor imaging or therapy, few are more available or desirable than Pb-203, 212 and Bi-212. Yet no clinical studies have as yet been possible solely due to the lability in vivo of known complexes. We now report that bismuth complexes of the ligands p-SCN-Bz-DOTA and p-SCN-Bz-trans-cyclohexylDTPA are effective at protecting Bi-206 from release when linked to immunoproteins. Practicable, efficient ligand syntheses will be reported. Initial studies reveal that antibody is labeled efficiently with radiolead DOTA complexes. Preliminary studies indicate stability in vivo.
The ion mobilities of |"2"1"1At|At(I) in dependence on thiourea (tu) concentration, iodide concentration and a mixture of both ligands were measured by the electromigration method in free electrolytes. An equilibrium model was developed for the characterization of electromigration curves which permitted the calculation of stability constants and ion mobilities of the complexes |AtI|, |AtI_2|"-, |Attu|"+, |Attu_2|"+ and |AtItu| existing in these solutions. Ethanol and water served as solvents. The temperature was 298 K and the ionic strength was about 0.05 mol/dm"3. (author) 16 refs.; 2 figs.
Metalloid cluster compounds of group 14 of the general formulae EnRm with n > m (E = Si, Ge, Sn, Pb; R = ligand), where naked as well as ligand bound tetrel atoms are present, represent a novel class of cluster compounds in group 14 chemistry and can be seen as intermediates on the way to the elemental state. Therefore, interesting properties are expected for these compounds, which might complement results from nanotechnology. In this article, first results for germanium are discussed, together with novel build-up reactions on the way to novel materials based on metalloid cluster compounds. GRAPHICAL ABSTRACT[image omitted
The stability constant values of Pa(V) with some complexing ligands (chloride, sulfate and oxalate) are graphically determined using solvent extraction data. The organic phase was at constant composition of HTTA in benzene while the aqueous phase was held at constant hydrogen ion concentration and ionic strength of 3. The curve-fitting method was adopted throughout this investigation, giving the following values. The stability constants obtained are used to calculate the distribution of the different Pa (V) species in the corresponding aqueous phase (expressed in mole fraction) as a function of ligand ion concentration.
The mechanistic aspects of electrochemical reductions of U"V"IO_2(acac)_2dmso(acac=acetylacetonate, dmso=dimethyl sulfoxide) complex with bidentate ligand(acac) in DMSO were investigated by using cyclic voltammetry, normal pulse voltammetry, and spectrophotometer equipped with an optical transparent thin layer electrode cell. It is concluded that the uranyl complexes with bidentate ligands at the equatorial plane form stable U(V) complexes by the electrochemical reduction and that their molar extinction coefficients in the visible region are very small. (J.P.N.).
The t-butyldimethylsilyl group is shown to be an ideal protecting group for the 2T-hydroxyl function of ribonucleosides during the synthesis of ribonucleotides using any of nine commonly used condensing...Full Text Available
The authors investigated the effect of T-2 toxin on rat liver mitochondrial protein synthesis. Isolated rat liver mitochondria were supplemented with an S-100 supernatant from rat liver and an external ATP-generating system. An in-vitro assay employing cycloheximide, and inhibitor of cytoplasmic protein synthesis, and chloramphenicol, and inhibitor of mitochondrial protein synthesis, to distinguish mitochondrial protein synthesis from the cytoplasmic process. Amino acid incorporation into mitochondria was dependent on the concentration of mitochondria and was inhibited by chloramphenicol. The rate of uptake of tritium leucine into mitochondrial protein was unaffected by the addition of T-2 toxin and was not a rate-limiting step in incorporation. However, 0.02 micrograms/ml of T-2 toxin decreased the rate of protein synthesis inhibition correlated with the amount of T-2 toxin taken ...
This work describes the synthesis and characterization of novel thermoresponsive highly-branched polyamidoamine-polyethylene glycol-poly (D, L-lactide) (PAMAM-PEG-PDLLA) core-shell nanoparticles....Full Text Available
The accepted model of retroviral reverse transcription includes a circular DNA intermediate which requires strand displacement synthesis for linearization and creation of an integration-competent, long...Full Text Available
An inexpensive, extremely rapid manual method for simultaneous synthesis of large numbers of oligodeoxyribonucleotides on 50 or 150 nanomole scale is described. The oligonucleotides are assembled in...Full Text Available
There is renewed interest in the +6 oxidation state of iron, ferrate (VI) (FeVIO42-), because of its potential as a benign oxidant for organic synthesis, as a chemical in developing cleaner ('greener') technology for remediation processes, and as an alternative for environment-friendly battery cathodes. This interest has led many researchers to focus their attention on the synthesis of ferrate(VI). Of the three synthesis methods, electrochemical, wet chemical and thermal, electrochemical synthesis has received the most attention due to its ease and the high purity of the product. Moreover, electrochemical processes use an electron as a so-called clean chemical, thus avoiding the use of any harmful chemicals to oxidize iron to the +6 oxidation state. This paper reviews the development of electrochemical methods to synthesize ferrate(VI). The approaches chosen by different laboratories to overcome some of ...
SummaryAn overview of recent progress on the total synthesis of acetogenins from Annonaceae during the past 12 years is provided. These include mono-tetrahydrofurans, adjacent bis-tetrahydrofurans,...Full Text Available
A new strategy is presented for the synthesis of graft copolymers using only the ring-opening metathesis polymerization (ROMP). From a ROMP-derived main chain, pendant maleimide functional groups...Full Text Available
Phosphoramidite reagents can phosphitylate guanine bases at the O6-position during solid phase synthesis and serious chain cleavage occurs if the base phosphitylation is not eliminated before the iodine/water...Full Text Available
Cell suspension cultures of tomato, Lycopersicon esculentum Mill. cv VFNT-Cherry, produce phytochelatins (poly[γ-glutamylcysteinyl]glycines) when exposed to cadmium. The synthesis...Full Text Available
Leucoplasts were isolated from the endosperm of developing castor (Ricinis communis) endosperm using a discontinuous Percoll gradient. The rate of fatty acid synthesis was highest...Full Text Available
Research programs, presented at the contractor's review meeting on indirect liquefaction, are presented on the following topics: oxygenates (methanol) synthesis; Fischer-Tropsch synthesis; product upgrading; and process support engineering evaluations. A total of 18 reports are included. Individual projects are processed separately for the data bases. (CBS)
Changes in RNA synthesis in liver nuclei were observed at different ages and after hypophysectomy and hormone replacement in female Sprague-Dawley rats. As determined by the incorporation of [3H]UMP...Full Text Available
Adenosine triphosphate (ATP) is an indicator of living biomass in marine particulates. This report details the method used by Lawrence Berkeley Laboratory to analyze particulate ATP in samples taken from oligotrophic, tropical ocean waters. It represents a synthesis of previously published methods.
Regulation of glucose isomerase synthesis was studied in Thermoanaerobacter strain B6A, which fermented a wide variety of carbohydrates including glucose, xylose, lactose, starch, and...Full Text Available
This study examined the hypothesis that solid surfaces may stimulate attached bacteria to produce exopolymers. Addition of sand to shake-flask cultures seemed to induce exopolymer synthesis by a number...Full Text Available
A short, highly stereoselective (over 97%) synthesis of all-trans squalene is described. Starting with succinaldehyde, a tetraenedichlorodione having the complete squalene skeleton...Full Text Available
4-methylumbelliferone (4-MU) is a hyaluronic acid (HA) synthesis inhibitor with anticancer properties; the mechanism of its anticancer effects is unknown. We evaluated the effects of 4-MU on...Full Text Available
The accumulation of α-1,4-polyglucans is an important strategy to cope with transient starvation conditions in the environment. In bacteria and plants, the synthesis of glycogen and starch occurs...Full Text Available
A new series of heteroleptic cyclometalated platinum(II) complexes Pt-1a-f was synthesized, employing 2-arylpyridine (or 1-arylisoquinoline) (HC{sup L}AMDAN-1) and 1,3-bis(3,4-dibutoxyphenyl)propane-1,3-dione (HO{sup L}AMDAO-1) for cyclometalation and as ancillary ligands, respectively, and photoluminescent properties were investigated. Focusing on red-shifted phosphorescence, C{sup L}AMDAN ligands containing pi-extended aromatics and electron-rich heterocycles were examined. All obtained complexes exhibited photoluminescence at ambient temperature, and the emission maxima ranged from green (lambda{sub PL}=518 nm) to far red (lambda{sub PL}=708 nm). The large Stokes shifts of more than 100 nm and sub-microsecond or microsecond emission lifetimes revealed that these complexes are phosphorescent emissive. The quantum yield of Pt-1 ranged from 0.02 to 0.59 at ambient temperature and decreased as the emission maximum was red-shifted. In comparison ...
Research continued on the synthesis of model compounds for coal liquefaction research. This report covers the actual laboratory investigation performed during the reporting period in order to attain the stated objective of the project, viz, the synthesis of a model compound containing tetrahydronaphthalene, naphthalene and phenyl moieties linked by methylene, ethylene and ether bonds. The overall synthetic approach aimed at obtaining the end product has been broken down into three major steps that involve the synthesis of three key reactive intermediates. These are: (1) 3,5-dimethyl-5-bromobenzyl chloride, (2) 1-chloromethylene-2-hydroxytetralin and (3) 2-chloromethylene-1-hydroxynaphthalene.
A mixture of aminoacids was irradiated by a scattered proton beam, its energy varying from 4 to 6.6 MeV, by doses up to 5 x 10"1"1 proton/cm"2 for studying the potentiality of abiogenic synthesis of biologically important compounds in space. It was ascertained that increase in the radiation dose and reduction of proton energy involve increase in effectiveness both of destruction of the initial aminoacid (tryptophan, tyrosine, glycine) and synthesis of the relevant dipeptide. Essential influence of mineral substrate on abiogenic synthesis of natural nucleotides under the action of diverse energy sources was pointed out
Total synthesis of cis-solamin A was accomplished without using protecting groups starting from (-)-muricatacin in 11 steps with an overall yield of 4.5%. The backbone of cis-solamin A was constructed by olefin cross-metathesis between the tetrahydrofuran moiety and g-lactone moiety. An enzymatic kinetic transesterification procedure was successfully applied to the synthesis of an optically pure g-lactone moiety.
We have recently shown the applicability of robotics to the synthesis of a positron-emitting radiopharmaceutical, namely 16#alpha#[F-18]fluoroestradiol-17#beta#, a breast tumor imaging agent. We now report the application of the robot to the synthesis of two additional radiopharmaceuticals, [F-18]spiroperiodol and [C-11]butanol. This achievement shows the power of a robot as a multifunctional automated device for the synthesis of several positron-emitting radiopharmaceuticals in limited laboratory space. (author).
We have found that the methionine repression of the ..beta..-subunit gene expression is not due to degradation of the ..beta..-subunit but is due to an effect on synthesis of the ..beta..-subunit. The effect of methionine on the synthesis of the ..beta..-is due to an inhibition of ..beta..-subunit mRNA synthesis. 3 references, 1 figure.
This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.
A novel, one-pot, multicomponent synthesis of 4-arylidene-3-methyl-1-(4-arylthiazol-2-yl)-1H-pyrazol-5(4H)-ones is described using phenacyl bromides, thiosemicarbazide, ethylacetoacetate, and aryl aldehydes. This synthesis involves simultaneous formation of two heterocycles like thiazole and pyrazolone along with condensation of active methylene group by aldehydes via Knoevenagel reaction. The methodology is mild, efficient, and high yielding. GRAPHICAL ABSTRACT[image omitted
Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ...
The p75 neurotrophin receptor (p75"N"T"R) is a death receptor which belongs to the tumor necrosis factor receptor super-family of membrane proteins. This study shows that p75"N"T"R retarded cell cycle progression by induced accumulation of cells in G0/G1 and a reduction in the S phase of the cell cycle. The rescue of tumor cells from cell cycle progression by a death domain deleted (#DELTA#DD) dominant-negative antagonist of p75"N"T"R showed that the death domain transduced anti-proliferative activity in a ligand-independent manner. Conversely, addition of NGF ligand rescued retardation of cell cycle progression with commensurate changes in components of the cyclin/cdk holoenzyme complex. In the absence of ligand, p75"N"T"R-dependent cell cycle arrest facilitated an increase in apoptotic nuclear fragmentation of the prostate cancer cells. Apoptosis of p75"N"T"R expressing cells occurred via the intrinsic mitochondrial ...
This study focuses on a series of Pt{sup II}(L-L{prime})(dppm){sup n+} complexes, where dppm is bis(diphenylphosphino)methane and L-L{prime} are C(caret)C{prime} (n = 0), C(caret)N (n = 1), and N(caret)N{prime} (n = 2) aromatic ligands. Structural characteristics are reported. Structural features indicate that the Pt-C bond distance is shorter than the Pt-N bond distance in symmetrical complexes and that the Pt-P bond distance trans to N is shorter than the Pt-P bond trans to C. This is consistent with the {sup 31}P NMR spectra where the chemical shift of the P trans to C is {approximately}10 ppm less than found for P trans to N. The energy maxima of the metal-to-ligand charge-transfer band for the complexes containing various L-L{prime} ligands occur in the near-UV region of the spectrum and fall into the energy series bpy > bph > phen > 2-phpy > 2-ptpy > 2-phq > 7,9-bzq, where bpy ...
The use of platinum(II) complexes as tags and probes for biomolecules is indeed advantageous for their reactivities can be selective for certain purposes through an interplay of mild reaction conditions and of the ligands bound to the platinum. The use of {sup 195}Pt NMR as a method of detecting platinum and its interactions with biomolecules was carried out with the simplest model of platinum(II) tagging to proteins. Variable-temperature {sup 195}Pt NMR spectroscopy proved useful in studying the stereodynamics of complex thioethers like methionine. The complex, Pt(trpy)Cl{sup +}, with its chromophore has a greater potential for probing proteins. It is a noninvasive and selective tag for histidine and cysteine residues on the surface of cytochrome c at pH 5. The protein derivatives obtained are separable, and the tags are easily quantitated and differentiated through the metal-to-ligand charge transfer bands which are sensitive to the ...
The thermostable Thermus aquaticus DNA polymerase (Taq Pol) has been the key factor in transforming the initial PCR method into one with huge impact in molecular biology and biotechnology. Therefore, the development of effective affinity adsorbents for the purification of Taq Pol, as well as other DNA polymerases, attracts the attention of the enzyme manufacturers and the research laboratories. In this report we describe a simple protocol for the purification of Taq Pol from E. coli lysates, leading to enzymes of high specific activity and purity. The protocol is based on a single affinity chromatography step, featuring an immobilized ligand selected from a structure-biased combinatorial library of dNTP-mimetic synthetic ligands. The ligand library was screened for its ability to bind and purify Taq Pol from E. coli lysates. One immobilized ligand (mABSGu) of the general formula X-Trz-Y, bearing ...
The IR spectra of complexes of uranyl perhalates with antipyrine (AP), hexamethylphosphorus triamide (HMPTA), dimethyl sulfoxide (DMSO), and water with the composition (UO/sub 2/L/eta/)(Ha10/sub 4/)/sub 2/, where Ha10/sub 4/ = C10/sub 4//sup -/, Bro/sub 4//sup -/, 10/sub 4//sup -/ (except for DMSO and H/sub 2/O), L is a neutral ligand, n = 4 for HMPTA and n = 5 for the remaining L, were investigated. X-ray crystallographic analysis established that the investigated perhalate complexes of uranyl with the same neutral ligands are isostructural. It was established that in the complexes studied the Ha10/sub 4//sup -/ anions are outer-sphere anions, and the value of the frequency of the antisymmetrical stretching vibration of the uranyl group does not depend on the nature of the perhalate anion. From the values obtained for ..nu../sub 3/ UO /SUP 2/2/ /sup +/, the values of the multiplicity and energy of the uranium-ligand bond ...
New Schiff base derivatives (L1 and L2) were prepared by the condensation of 2-hydroxy-3-methoxybenzaldehyde (o-vanillin) and 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with 5-methylfurfurylamine. Two new complexes [Ni(L1)2] and [Cu(L1)2] have been synthesized with bidentate NO donor Schiff base ligand (L1). The Ni(II) and Cu(II) atoms in each complex are four coordinated in a square planar geometry. Schiff bases (L1 and L2) and complexes [Ni(L1)2] and [Cu(L1)2] were characterized by elemental analyses, FT-IR, UV-vis, mass and 1H, 13C NMR spectroscopies. The crystal structures of the ligand (L2) and complexes [Ni(L1)2] and [Cu(L1)2] have also been determined by using X-ray crystallographic technique.
The thiazolidinedione (TZD) or glitazone class of peroxisome proliferator-activated-#gamma# (PPAR-#gamma#) ligands not only induce adipocyte differentiation and increase insulin sensitivity, but also exert growth inhibitory effects on several carcinoma cell lines in vitro as well as in vivo. In the current study the in vitro effect of four PPAR-#gamma# agonists (ciglitazone, pioglitazone, troglitazone, rosiglitazone) on the cell growth of seven human neuroblastoma cell lines (Kelly, LAN-1, LAN-5, LS, IMR-32, SK-N-SH, SH-SY5Y) was investigated. Growth rates were assessed by a colorimetric XTT-based assay kit. Expression of PPAR-#gamma# protein was examined by immunohistochemistry and Western blot analysis. All glitazones inhibited in vitro growth and viability of the human neuroblastoma cell lines in a dose-dependent manner showing considerable effects only at high concentrations (10 #mu#M and 100 #mu#M). Effectiveness of the glitazones on neuroblastoma cell growth ...
The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni{sup 2+} ion in isostructural nickel halide crystals NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2}. The parameters of the crystal field acting on the Ni{sup 2+} ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni{sup 2+} ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI{sub 2}>NiBr{sub 2}>NiCl{sub 2}.
The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni"2"+ ion in isostructural nickel halide crystals NiCl_2, NiBr_2, and NiI_2. The parameters of the crystal field acting on the Ni"2"+ ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni"2"+ ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI_2>NiBr_2>NiCl_2.
An /alpha//sub 2/-adrenergic receptor subtype has been cloned from a human kidney cDNA library using the gene for the human platelet /alpha//sub 2/-adrenergic receptor as a probe. The deduced amino acid sequence resembles the human platelet /alpha//sub 2/-adrenergic receptor and is consistent with the structure of other members of he family of guanine nucleotide-binding protein-coupled receptors. The cDNA was expressed in a mammalian cell line (COS-7), and the /alpha//sub 2/-adrenergic ligand (/sup 3/H)rauwolscine was bound. Competition curve analysis with a variety of adrenergic ligands suggests that this cDNA clone represents the /alpha//sub 2/B-adrenergic receptor. The gene for this receptor is on human chromosome 4, whereas the gene for the human platelet /alpha//sub 2/-adrenergic receptor (/alpha//sub 2/A) lies on chromosome 10. This ability to express the receptor in mammalian cells, free of other adrenergic receptor subtypes, should help ...
The future use of single-molecule magnets in applications will require the ability to control and manipulate the spin state and magnetization of the magnets by external means. There are different approaches to this control, one being the modification of the magnets by adsorption of small ligand molecules. In this paper we use iron phthalocyanine supported by an Au(111) surface as a model compound and demonstrate, using x-ray photoelectron spectroscopy and density functional theory, that the spin state of the molecule can be tuned to different values (S #approx# 0, 1/2, 1) by adsorption of ammonia, pyridine, carbon monoxide or nitric oxide on the iron ion. The interaction also leads to electronic decoupling of the iron phthalocyanine from the Au(111) support. (fast track communication)
SummaryExperimental evidence has demonstrated the importance of FGF signalling in morphogenesis of the mandibular processes. FGFs transmit their signals through four tyrosine kinase transmembrane receptors (FGFRs). Alternative splicing in FGFRs including FGFR2 generates different isoforms that exhibit different ligand-specificities, exclusive tissue distributions and specific biological functions. Despite extensive information regarding the isoform-specific patterns of expression Fgfr2c and Fgfr2b during morphogenesis of many organs, a comparative analysis of these specific isoforms in the chick mandible has not been reported. To better understand the function of FGFR2 in mandibular morphogenesis, we have analysed the expression Fgfr2b, Fgfr2c and their putative ligands Fgf10 and Fgf9, in ...
The extraction-spectrophotometric method has been used to study lanthanoid ion complexing (Pr, Nd, Ho and Er) with antipyrine (Ant) and salicylic acid (Sal). The component relationship in different-ligand compounds Ln:Aut:Sal=2:3:6 and solvate number equal to 5 are determined; molar extinction coefficients of binary and different-ligand compounds are calculated. Oscillator strengths of absorption bands corresponding to supersensitive transitions of neodymium, holmium, erbium and some most intensive praseodymium bands are calculated. The study of IR spectra of investigated compounds allows to conclude on formation of coordination bonds of the central atom with the antipyrine molecule through the oxygen of the carbonyl group as well as on carboxyl group hydrogen substitution for metal and formation of coordination bond with OH group in salicylic acid molecules.
The recent acceleration of effort to elucidate and explore the coordination chemistry of technetium has been prompted mainly by the need for a new generation of radiotracers in nuclear medicine, preferentially for tomograhic studies. Current approaches and their limitations in designing "9"9"mTc complexes capable of penetrating cell membranes of the target organs, and remaining there sufficiently long, are reviewed. With the predominance of Tc(V) oxo compounds, especially for brain imaging agents, new N4 and N2S2 coordinate complexes have been developed by shifting from bidentate to tetradentate ligands with a variable side chain or other adjustable reactivity. The search for myocardial imaging agents has focused on a variety of mixed ligand complexes of Tc(III) and most promising [Tc(CNR)_6]"+ complexes of Tc(I). 64 refs. (author).
Previous studies from this laboratory have shown that certain N-substituted phthalimides (NSPs) exhibit GA-like activity in a range of specific bioassays and that bioactive NSPs compete with ({sup 3}H)-GA{sub 4} for soluble binding sites in cucumber homogenates. As such, these compounds may prove useful in the purification and characterization of GA receptor proteins. To this end, five azido-NSPs have been synthesized and are currently being screened for biological activity and photochemical stability. Three azido-NSPs elicit {alpha}-amylase production in barley half-seeds and stimulate tissue elongation in d{sub 5} maize, lettuce, sunflower, and soybean. Further evaluations are in progress and these data as well as the utility of these compounds as photo-affinity ligands will be discussed.
1,3-Dienes derived from steroidal D-ring C17-ketones undergo Ni(II)-catalyzed hydrovinylation to give 1,2- or 1,4-addition of ethylene. Using finely tuned phosphoramidite ligands it is possible to synthesize either the C20 (R)- or the C20 (S)-derivatives without mutual contamination. The proportion of the 1,4-adduct, which is also formed stereoselectively, can be minimized by optimizing the reaction conditions. Since the two alkenes in the resultant dienes have differing steric demands for many potential reactions, and are ideally juxtaposed for further D-ring functionalization, these intermediates could be useful for the preparation of biologically important compounds such as vitamin D analogs and various antitumor steroidal glycosides.
A detailed comparison of the softness of gold and silver has been reported in the light of hard soft acid base (HSAB) principle. Gold and silver nanoparticles in organic media (i.e., organosol) have been exploited individually to establish the principle. Sulfur and nitrogen were employed as soft and borderline donating atoms to examine the metal-ligand interactions. In this regard, thiols and amines have been considered as interacting ligands with sulfur and nitrogen donor atoms respectively. The stronger affinity of gold towards softer sulfur donor as compared to nitrogen and conversely a reasonable interaction of silver nanoparticles with both the atoms authenticate the softer nature of gold nanoparticle as compared to silver one.
Single-crystalline cadmium selenide nanoparticles were obtained using high-temperature solution phase synthesis (HTSPS) synthesis. X-Ray powder diffraction and transmission electron microscopy were used to confirm the crystallinity and morphology of the resulting nanoparticles. To study the action of CdSe on antioxidant activity, we selected two biotechnological important strains of microalgae: cyanobacteria Spirulina platensis and red microalgae Porphyridium cruentum. In the case of Porphyridium cruentum, the obtained results demonstrated an increase in the productivity. For Spirulina platensis, the presence of the compound in the cultivating medium decreased the productivity of cyanobacteria.
Carbon monoxide, H{sub 2}, and CO{sub 2} in synthesis gas can be converted to CH{sub 4} by employing a triculture of Rhodospirillum rubrum, Methanosarcina barkeri, and Methanobacterium formicicum. Trickle-bed reactors have been found to be effective for this conversion because of their high mass-transfer coefficients. This paper compares results obtained for the conversion of synthesis gas to CH{sub 4} in 5-cm- and 16.5-cm-diameter trickle-bed reactors. Mass-transfer and scale-up parameters are defined, and light requirements for R. rubrum are considered in bioreactor design.
Cyst nematodes are troublesome parasites that live on, and destroy, a range of important host vegetable plants. Damage caused by the potato cyst nematode has now been reported in over 50 countries. One approach to eliminating the problem is to stimulate early hatching of the nematodes, but key hatching stimuli are not naturally available in sufficient quantities to do so. Here, we report the first chemical synthesis of solanoeclepin A, the key hatch-stimulating substance for potato cyst nematode. The crucial steps in our synthesis are an intramolecular cyclization reaction for construction of the highly strained tricyclo[5.2.1.01,6]decane skeleton (DEF ring system) and an intramolecular Diels???Alder reaction of a furan derivative for the synthesis of the ABC carbon framework. The present ...
Hyaluronan (HA), a non-sulfated glycosaminoglycan, is widely used in the clinic for viscosurgery, viscosupplementation, and treatment of osteoarthritis. Four decades of chemical modification...Full Text Available
Iodine-125 labelled vinyl and aryl iodides are formed via the reaction of sodium iodide-125 with vinyl- and arylboronic acids. Good yields of isomerically pure products are obtained.
...Synthesis of low-temperature, fast, single-firing body for porcelain stoneware tiles with coal gangue Synthesis of low-temperature, fast, single-firing body for porcelain stoneware ... tiles with coal gangue Synthesis of low-temperature, fast, single-firing body for porcelain stoneware tiles with coal gangue Wei et al.,... Article Synthesis of low-temperature, fast, single-firing body for porcelain stoneware tiles with coal gangue Qiangwei Wei1, Wenyuan Gao1*, and Xinguo ...According to phase diagram theory, a low-temperature, fast, single-firing body mix for porcelain stoneware tiles was designed in the quaternary system CaO-MgO-Al2O3-SiO2, using ...
... Here we will summarize the synthesis, structure activity relationships , and molecular sites of action of mGluR5 PAMs. We will also review preclinical studies ...
Proteins are polymers of amino acids. These macromolecules are synthesized by intracellular machines called {\\it ribosome}. Although, traditionally, the experimental investigation of protein synthesis has been an active area of research in molecular cell biology, important quantitative models of this phenomenon have been reported mostly in the research journals devoted to statistical physics and related interdisciplinary topics. From the perspective of a physicist, protein synthesis is a phenomenon of {\\it classical transport of interacting ribosomes on a messenger RNA (mRNA) template} that dictates the sequence of the amino acids on the protein. Here we bring this frontier area of contemporary research into the classroom by appropriate simplification of the models and methods. In particular, we develope a simple toy model and analyze it by some elementary techniques of non-equilibrium statistical mechanics to predict the average rate of ...
Metastable yttrium-oxide films are synthesized using reactive sputter deposition. The yttrium concentration of the as-deposited film is found to vary as a function of the sputter deposition rate. In addition to the synthesis of the cubic equilibrium phase...
Synthesis of wild-type Neurospora crassa assimilatory nitrate reductase is induced in the presence of nitrate ions and repressed in the presence of ammonium ions. Effects of several...Full Text Available
Hie synthesis of diverse biologically important compounds, under condi- tions which existed on the earth in the initial period of its evolution, ha; ...
Objective and sourcesWe reviewed the epidemiologic literature for PFOA.Data synthesisPerfluorooctanoic acid (PFOA) does not occur naturally but is...Full Text Available
... 4? Program History 5? Center for Advanced Materials and Smart Structures 6? Center for Systems ... Systems 14? Center for Photonic Materials Research 15? Synthesis, Manufacturing and Characterization ...
Cambridge scientists in the late 1980's. This same team, then headed by Professor John Baldwin, built the world's first separated-element optical/infrared aperture synthesis...
SummaryA microreactor for electrochemical synthesis has been designed and fabricated. It has been shown that different reactions can be carried out successfully using simple protocols.
Transforming growth factor (TGF)-beta isoforms (TGF-beta 1, -beta 2, and -beta 3) regulate cell growth and differentiation and have critical regulatory roles in the process of tissue repair and remodeling....Full Text Available
We have studied the self-association reactions of purified GDP-liganded tubulin into double rings and taxoid-induced microtubules, employing synchrotron time-resolved x-ray solution scattering. The...Full Text Available
Stability constants for uranium-tetracycline complexes were determined by the method of average number of ligands, the method of limiting values, the method of two parameters and the method of weighted least squares. Solvent extraction technique was used to obtain experimental data. (author). 10 refs.; 5 figs.
σ-Receptor (σR) antagonists have been reported to block certain effects of psychostimulant drugs. The present study examined the effects of σR ligands in rats trained to self-administer...Full Text Available
Dithiolato-nickel complexes with multisulfur ligands derived from benzenehexathiolate have been synthesized. The properties of the monomeric and polymeric complexes have been characterized by ESR spectroscopic and magnetochemical data and by electrical conductivity measurements. The prepared complexes are paramagnetic and have characteristic absorptions between 800 and 1000 nm. (orig.).
The retinoic acid receptor-related orphan receptors α and γ (RORα (NR1F1) and RORγ (NR1F3)) are orphan nuclear receptors and perform critical roles in regulation of development,...Full Text Available
We have shown that addition of exogenous delta-aminolaevulinic acid (ALA) to rat pancreatoma AR4-2J cells in culture leads to the increased production of porphobilinogen (PBG) and the accumulation of...Full Text Available
Translocator protein (TSPO) is upregulated in activated microglia and thus can serve as a marker of neuroinflammation. Recently, a novel radioligand, 11C-N,N-diethyl-2-[2-(4-methoxyphenyl)-5,7-dimethyl-pyrazolo[1,5-a]pyrimidin-3-yl]-acetamide...Full Text Available
LRP1 is a type-1 transmembrane receptor that mediates the endocytosis of diverse ligands. LRP1 β-chain proteolysis results in release of sLRP1 that is present in human plasma. In this study,...Full Text Available
The immunolocalization of the low density lipoprotein receptor-related protein 1 (LRP1) and its ligand alpha 2-Macroglobulin (α2M) was examined in tissues from human donor...Full Text Available
/sup 125/I-Calmodulin is internalized by isolated rat renal brush border membrane vesicles (BBV) in a time, temperature and calcium dependent manner. Internalization of /sup 125/I-calmodulin into the osmotically sensitive space of BBV was distinguished from binding of the ligand to the outer BBV surface by examining the interaction of ligand and BBV at different medium osmolarities (300-1100 mosm), uptake was inversely proportional to medium osmolarity. Internalized /sup 125/I-calmodulin was intact and Western blots of solubilized BBV with /sup 125/I-calmodulin demonstrated the presence of several calmodulin-binding proteins of 143, 118, 50, 47.5, 46.5 and 35 kilodaltons which could represent potential intravesicular binding sites for the ligand. Heparin and the related glycosaminoglycan heparin sulfate both showed a dose-dependent inhibition (0.5-50 ..mu..g/ml) of /sup 125/I-calmodulin uptake by BBV, but other sulfated and ...
PlGF, one of the ligands for VEGFR-1, has been implicated in tumor angiogenesis. However, more recent studies indicate that genetic or pharmacological inhibition of PlGF signaling does not result in...Full Text Available
The purpose was to develop a simplified and reliable method of separating free from antibody-bound ligand using a precipitating antibody linked to a cellulose derivative. Dose-response curves and control sera were set up in parallel for various pituitary and placental polypeptides, steroid hormones, insulin, glucagon, triiodothyronine, thyroxine, angiotensin I, calcitonin, gastrin, cyclic AMP, and digoxin. After first-antibody reactions had reached equilibrium, free and bound ligand were separated using a double-antibody solid-phase system in parallel with conventional methods, including dextran-coated charcoal, double-antibody precipitation, single-antibody solid phase, organic solvents, salt precipitation, and anion-exchange resins. The effect of variations in temperature, incubation time, protein content, pH, and amount of separating material added were studied. The results showed that separation was complete within 1 hr for small ...
The purpose was to develop a simplified and reliable method of separating free from antibody-bound ligand using a precipitating antibody linked to a cellulose derivative. Dose-response curves and control sera were set up in parallel for various pituitary and placental polypeptides, steroid hormones, insulin, glucagon, triiodothyronine, thyroxine, angiotensin I, calcitonin, gastrin, cyclic AMP, and digoxin. After first-antibody reactions had reached equilibrium, free and bound ligand were separated using a double-antibody solid-phase system in parallel with conventional methods, including dextran-coated charcoal, double-antibody precipitation, single-antibody solid phase, organic solvents, salt precipitation, and anion-exchange resins. The effect of variations in temperature, incubation time, protein content, pH, and amount of separating material added were studied. The results showed that separation was complete within 1 hr for small ...
Human Fas/Apo-1 is a cell-surface protein that mediates apoptosis upon ligation with Fas ligand. The gene lies on the long arm of chromosome 10, consists of nine exons, and spans more than 26 kb of...Full Text Available
The p90 ribosomal S6 kinases (RSKs) also known as MAPKAP-Ks are serine/threonine protein kinases that are activated by ERK or PDK1 and act as downstream effectors of mitogen-activated protein kinase...Full Text Available
Following infection with the protozoan parasite Leishmania major, C57BL/6 mice develop a small lesion that heals spontaneously. Resistance to infection is associated with the development...Full Text Available
The DNA-binding properties of Ru(bpy)2(eilatin)2+ have been investigated to determine if the sterically expansive eilatin ligand confers specificity for destabilized single-base...Full Text Available
BackgroundAberrant CD40 ligand (CD154) expression occurs on both T cells and B cells in human lupus patients, which is suggested to enhance B cell CD40 signaling and play a role...Full Text Available
Amphiphilic pincer palladium complexes bearing hydrophilic and hydrophobic side chains on the planar NCN palladium pincer backbone were designed and prepared via the ligand introduction route. The complexes self-assembled under aqueous conditions to form vesicles with bilayer membranes containing palladium species. The catalytic activity of the vesicles in the Miyaura-Michael reaction in water was investigated. PMID:21837316
Amyloid plaques are a characteristic feature in Alzheimer’s disease (AD). A novel non-toxic contrast agent is presented, Gd-DTPA-K6Aβ1–30, which is homologous to Aβ,...Full Text Available
Only 15mol% of l-proline in ethanol proved to be a very efficient catalyst for the one-pot synthesis of a wide variety of highly substituted pyridines at room temperature. The methodology is mild, efficient, high yielding, and the products can be directly recrystallized from hot ethanol.
Synthesis of silver nanoparticles based on a polyol process and variable frequency microwave (VFM) was investigated. Comparing to a thermal method, the reaction by VFM radiation was much faster. The effects of silver nitrate concentration, poly(N-vinylpyrrolidone) (PVP) concentration, reaction time and reaction temperature were studied. It was found that the higher concentration of silver nitrate, longer reaction time and higher temperature increased the particle size while the higher concentration of PVP decreased the particle size.
This article describes the utilization of plastic wastes in a blast furnace. The plastic waste is a substitution for petroleum and coal as a raw material for synthesis gas production. The synthesis gas is the reducing agent in the blast furnace for the reduction of iron ores. You can find here an ecological and economical analysis of this process in comparison to the utilization of petroleum and coal. (SR)
A decoupled characteristic between the damping of a specific swing mode and the stabilizer gain of the corresponding machine in multimachine power systems is identified. Using this decoupled characteristic a power system stabilizer (PSS) synthesis approach which is based on the phase compensation concept is verified on a 9-machine system and the dynamic performance of this system is significantly improved. This method is proved to be effective, simple and it can provide useful guidance for the PSS field tuning.
The purpose of work is systematical studying of benzo (B) of thiophene-1,1-dioxides and their 2,3-di-hydro derivatives behaviour in the reactions of electrophflic, radical, nucleophilic nitration, reduction of nitro group, embodiment of synthesis of N-amino derivatives, investigation of sulfur containing hetero-cyclic compounds, including of residues of some steroids
Synthesis of the azido substituted non-steroidal anti-inflammatory drug 2-(2,6-dichloroanilino)phenylacetic acid and isotope labeling of this compound have been performed and are described. Initial evaluation of the binding ability and photoreactivity indicates that this compound has potential for photoaffinity labeling as well as enzyme selectivity studies. (author).
The synthesis of novel b-functionalized derivatives of the clinically used photosensitizer Temoporfin has been achieved by nucleophilic addition reactions to a corresponding diketo chlorin. The b-substituted dihydroxychlorin products exhibit a strong absorption in the red spectral region, a high singlet oxygen quantum yield, and were found to be highly effective in in vitro assays against HT-29 tumor cells.
The synthesis of (/sup 14/C)-10,11-Epoxy-(2E,6E)-farnesyl diazoacetate in one vessel, starting from (/sup 14/C)-glyoxylic acid, is described. This compound is useful as a potential photoaffinity labeling agent for juvenile hormone binding sites.
With the aim of an experimental check on the validity of the theory of molecular recognition, the authors have carried out the chemical-enzymatic synthesis and cloning of the gene of human calcitonin and also of the genes of antisense polypeptides to human calcitonin and miniproinsulin. It has been shown that recombinant plasmids obtained on the basis of these synthetic genes are capable of ensuring the biosynthesis of the given polypeptides in E. coli cells as hybrid proteins with the IgG-binding domain of staphylococcal protein A.
We recently found that injection of 2 mCi of yttrium 90 (90Y; approximately 23,000 rads) into normal canine knees stimulated glycosaminoglycan (GAG) synthesis by femoral condylar cartilage. The present investigation was conducted to determine whether radiation affects cartilage metabolism directly. Rates of GAG synthesis and degradation in normal canine articular cartilage were studied following irradiation. Cultured synovium from the same knees was treated similarly, to determine the effects of irradiation on hyaluronic acid synthesis. Twenty-four hours after exposure to 1,000 rads, 10,000 rads, or 50,000 rads, 35S-GAG synthesis by the cartilage was 93%, 69%, and 37%, respectively, of that in control, nonirradiated cartilage. The effect was not rapidly reversible: 120 hours after exposure to 50,000 rads, GAG synthesis remained at only 28% of the control level. Autoradiography ...
Stable strange quark matter produced in the QCD phase transition in the early universe will trap neutrons and repel protons, thus reducing primordial helium production, Ysub(p). For reasonable values of Ysub(p), the radius of strange droplets must exceed 10/sup -6/ cm if strange matter shall solve the dark-matter problem without spoiling Big Bang helium synthesis. (orig.).
Stable strange quark matter produced in the QCD phase transition in the early universe will trap neutrons and repel protons, thus reducing primordial helium production, Ysub(p). For reasonable values of Ysub(p), the radius of strange droplets must exceed 10/sup 6/ cm if strange matter shall solve the dark-matter problem without spoiling Big Bang helium synthesis. (orig.).
OBJECTIVES: To assess the suitability of analyzing functional images of brain serotonin (5-HT) synthesis with statistical parametric mapping (SPM), and to investigate further possible sex-related regional...Full Text Available
The rates of synthesis of a class of both secreted and intracellular degradative enzymes in Bacillus subtilis are controlled by a signal transduction pathway defined by at least four regulatory genes:...Full Text Available
Partial Contents: Ternary Compounds; Granular Superconductors; Superconductivity in (SN)x and its Halogen Derivative (SNBr0.4)x; Studies of cuCl at Elevated Pressures; Superconducting Properties of Hydride Systems; Thin Film Superconducting Materials Research; Synthesis of Superconducting Nb3Si using High Pressures; Synthesis of Unstable A-15 Compounds by Epitaxial Recrystallization of Ion Implanted Layers; and Sputtering of Nb3Si.
The endogenous reverse transcriptase reaction of equine infectious anemia virus (EIAV) has been studied, and conditions allowing synthesis of full-length minus-strand DNA have been determined. In contrast...Full Text Available
The first enzyme-catalyzed reaction leading from indole-3-acetic acid (IAA) to the myo-inositol esters of IAA is the synthesis of indole-3-acetyl-1-O-β-d-glucose...Full Text Available
Expression of brome mosaic virus (BMV) coat protein and internal genes of many other positive-strand RNA viruses requires initiation of subgenomic mRNA synthesis from specific internal sites on minus-strand...Full Text Available
The extracellular matrix (ECM) of the distal tissues in a newt limb stump is completely reorganized in the 2-3-week period following amputation. In view of numerous in vitro studies showing that extracellular material influences cellular migration and proliferation, it is likely that the changes in the limb's ECM are important activities in the process leading to regeneration of such limbs. Using biochemical, autoradiographic, and histochemical techniques we studied temporal and spatial differences in the synthesis of glycosaminoglycans (GAGs) during the early, nerve-dependent phase of limb regeneration. Hyaluronic acid synthesis began with the onset of tissue dedifferentiation, became maximal within 1 weeks, and continued throughout the period of active cell proliferation. Chondroitin sulfate synthesis began somewhat later, increased steadily, and reached very high levels during chondrogenesis. During the first 10 days ...
Ternary copper(II) complexes [Cu(L1)B](ClO4) (1, 2) and [Cu(L2)B](ClO4) (3, 4), where HL1 and HL2 are tridentate NSO- and ONO-donor Schiff bases and B is a heterocyclic base, viz. dipyrido[3,2-d:2',3'-f]quinoxaline (dpq, 1 and 3) or dipyrido[3,2-a:2',3'-c]phenazine (dppz, 2 and 4), were prepared and their DNA binding and photoinduced DNA cleavage activity studied. Complex 1, structurally characterized by single-crystal X-ray crystallography, shows an axially elongated square-pyramidal (4 + 1) coordination geometry in which the monoanionic L1 binds at the equatorial plane. The NN-donor dpq ligand exhibits an axial-equatorial binding mode. The complexes display good binding propensity to calf thymus DNA, giving a relative order 2 (NSO-dppz) > 4 (ONO-dppz) > 1 (NSO-dpq) > 3 (ONO-dpq). They cleave supercoiled pUC19 DNA to its nicked circular form when treated with 3-mercaptopropionic acid (MPA) by formation of hydroxyl radicals as the cleavage active species ...
We have used a cell-free polymerase I transcription system derived from HeLa cells to study the regulation of human rRNA synthesis. Analysis of deletion mutants spanning the start site of transcription at nucleotide +1 indicates that the control region affecting initiation of human rRNA synthesis is contained within sequences from nucleotides -158 to +18. This promoter region can be subdivided into (i) a central segment of approximately 40 base pair that is required for transcription and (ii) flanking sequences that influence the efficiency of transcription in vitro. We have examined the in vitro transcriptional activity of the human extract under various conditions that are thought to modulate rRNA synthesis in vivo. Cell-free extracts prepared from HeLa cells infected with adenovirus 2 synthesize human rRNA at levels greatly decreased relative to uninfected cell extracts. By contrast, in vitro transcription of human rRNA ...
Spot 14 (S14) is a protein that is abundantly expressed in lipogenic tissues and is regulated in a manner similar to other enzymes involved in fatty acid synthesis. Deletion of S14 in mice decreased lipid synthesis in lactating mammary tissue, but the mechanism of S14's action is unknown. Here we present the crystal structure of S14 to 2.65 {angstrom} and biochemical data showing that S14 can form heterodimers with MIG12. MIG12 modulates fatty acid synthesis by inducing the polymerization and activity of acetyl-CoA carboxylase, the first committed enzymatic reaction in the fatty acid synthesis pathway. Coexpression of S14 and MIG12 leads to heterodimers and reduced acetyl-CoA carboxylase polymerization and activity. The structure of S14 suggests a mechanism whereby heterodimer formation with MIG12 attenuates the ability of MIG12 to activate ACC.
Study Design Best evidence synthesis. Objective To undertake a best evidence synthesis of the published evidence on the burden and determinants of neck pain and its associated disorders in the general population. Summary of Background Data The evidence on burden and determinants of neck has not previously been summarized. Methods The Bone and Joint Decade 2000?2010 Task Force on Neck Pain and Its Associated Disorders performed a systematic search and critical review of literature published between 1980 and 2006 to assemble the best evidence on neck pain. Studies meeting criteria for scientific validity were included in a best evidence synthesis. Results We identified 469 studies on burden and determinants of neck pain, and judged 249 to be scientifically admissible; 101 articles related to...
Plants use multiple defence mechanisms comprising both constitutive and inducible barriers to prevent entering of phytopathogenic micro-organisms. In many plant species one of the most efficient responses to combat attacking microbes is the rapid synthesis of antimicrobial low molecular weight phytoalexins, for example, resveratrol, 3,5,4prime-trihydroxystilbene (1). Resveratrol and its natural derivatives, however, display only moderate antimicrobial effects. Nevertheless, resveratrol may be a useful lead structure for the chemical synthesis of antimicrobials. In this study, several series of stilbenes have been synthesized, starting from the aldehydes using Wittig reactions to access the corresponding styrenes that were subjected to Mizoroki-Heck reactions to yield the stilbenes in good ...
The condensation reaction of furfural (F) on acetone (Ac) gives a high added value product, the 4-(2-furyl)-3-buten-2-one (FAc), used as aroma in alcohol free drinks, ice, candies, gelatines and other products of current life. This synthesis valorises the residues of sugar cane treatment since furfural is obtained by hydrolysis of sugar cane bagasse followed by vapor training extraction. In the face of numerous and complex reactions involved in this synthesis, it is very complicated to define the kinetic laws from exact stoichiometry. A solution allowing to cope the problem consists in identifying an appropriate stoichiometric model. It does not attempt to represent exactly all the reaction mechanisms, but proposes a mathematical support to integrate available knowledge on the transformati...
The use of Sialon ceramics has been restricted by the high temperature required for synthesis and the expense of the pure oxide and nitride raw materials required. For refractory applications the purity required is less demanding and it has been possible to exploit the outstanding durability of the Sialons at moderate cost. New low cost manufacturing routes are being developed by nitriding silicon metal powder at relatively low temperature with clay and various additives depending on the Sialon required. For example the introduction of carbon or fine silicon carbide allows the preparation of beta Sialons and alpha Sialons which can be stabilised by including the appropriate cations. A wide range of composite Sialon bodies with diverse properties can be prepared by a one step process. Current projects developing the synthesis routes are aimed, in the first instance, at refractory manufacture but are showing promise for more sophisticated ...
Current studies in plants suggest that the content of the coenzyme NAD is variable and potentially important in determining cell fate. In cases that implicate NAD consumption, re-synthesis must occur to maintain dinucleotide pools. Despite information on the pathways involved in NAD synthesis in plants, the existence of a mitochondrial nicotinamide mononucleotide adenylyltransferase (NMNAT) activity which catalyses NAD synthesis from nicotinamide mononucleotide (NMN) and ATP has not been reported. To verify the latter assumed pathway, experiments with purified and bioenergetically active mitochondria prepared from tubers of Jerusalem artichoke (Helianthus tuberosus L.) were performed. To determine whether NAD biosynthesis might occur, NMN was added to Jerusalem artichoke mitochondria (JAM)...
With the assistance of mechanical activation, yttrium-stabilized #alpha#-SiAlON was prepared by combustion synthesis in air, instead of high-pressure N_2 atmosphere for the first time. The reaction activity of metallic particles was remarkably enhanced by mechanical activation, which conduced the reduction of grain size, increased the total surface area and formation of fresh surface. The formation of #alpha#-SiAlON by combustion synthesis in air was explained by a kinetically induced reaction mechanism, in which both initial formation of #alpha#-SiAlON and following avoidance of oxidation were fulfilled by the retardation of O_2 infiltration owing to the short reaction period and fast cooling rate.
Super light and high performance Mg{sub 2}Si/Mg composites, which had excellent mechanical properties, were developed via the combination of solid-state synthesis and hot extrusion process. In this study, cold compacting (CP) and repeated plastic working (RPW) were firstly carried out for the mixture of Mg-Si powders, and the refinement of both Mg grains and dispersoids. Each specimen was evaluated by observation of microstructure and tensile test. As a result, it was understood that Mg{sub 2}Si dispersoids were refined and dispersed into Mg matrix, and were flowed along extrusion direction. And their mechanical properties were higher than the conventional die casting alloys. Also the effect of RPW as the improvement of properties and the decrease of synthesis temperature were confirmed. (orig.)
Logic Programming languages and combinational circuit synthesis tools share a common "combinatorial search over logic formulae" background. This paper attempts to reconnect the two fields with a fresh look at Prolog encodings for the combinatorial objects involved in circuit synthesis. While benefiting from Prolog's fast unification algorithm and built-in backtracking mechanism, efficiency of our search algorithm is ensured by using parallel bitstring operations together with logic variable equality propagation, as a mapping mechanism from primary inputs to the leaves of candidate Leaf-DAGs implementing a combinational circuit specification. After an exhaustive expressiveness comparison of various minimal libraries, a surprising first-runner, Strict Boolean Inequality "<" together with constant function "1" also turns out to have small transistor-count implementations, competitive to NAND-only or NOR-only libraries. As a practical outcome, a ...
Geometry optimizations of the quinoline-based platinum (II) complexes (1-R, 2-R) and their related calculations on excited state energies, electronic absorption spectra and orbital populations have been carried out by the hybrid density functional theory (DFT) and its time-dependent approach (TD-DFT). The solvent effects on excitation energies are taken into account using the conductor-like polarizable continuum model (C-PCM). The red-shifted level of absorption bands, energy gaps between the singlet ground state (S1) and the first triplet excited state (T1) for each examined complex have been elaborated thoroughly as well. We find that the quinoline-8-thoil (ligand 2) induces much more significant red-shifted level than 8-hydroxyquinoline (ligand 1), and singlet-triplet splitting energy g...
The authors have been involved for the last few years in developing high affinity sigma-receptor-specific radiopharmaceuticals for use in nuclear medicine. They recently demonstrated that sigma-1 receptors are expressed in human melanoma cells and that sigma receptors could be used as external markers for non-invasive imaging. In order to determine the presence of sigma receptors in other human tumors they have screened numerous non-small cell lung carcinoma, melanoma and breast cancer cell lines. All of these cell lines expressed high sigma receptor densities using commercially available ["3H]-(+)-pentazocine or ["3H]DTG tritiated sigma ligands. Therefore, a sigma ligand with high affinity in both sigma-1 and sigma-2 subtype pharmacological assays could be potentially useful for imaging a variety of primary and metastatic sites of various origins. The authors describe recent efforts to develop high affinity sigma radiopharmaceuticals and ...
Ultraviolet (UV) photoirradiation of Ag(I) compounds in the presence of an aqueous Triton X-100 solution has been exploited for the first time to prepare reproducible yellow silver hydrosol. The evolution of nanosized silver particles has been examined critically under the influence of different anions/ligands. Hence, time dependent evolution of silver hydrosol from different silver compounds in micelle via photochemical reduction is observed. Anions/ligands of precursor salts have been found to show profound influence (due to electron scavenging property, solubility, stability etc.) on the evolution route and efficiency of photochemical reduction of Ag(I) to Ag(O) in micelle and thereby classification of silver compounds becomes possible. Kinetic results reveal that the formation of silver particles proceeds via autocatalytic growth mechanism. The observed variation in rate constant values for the evolution of nanoparticles from different ...
The first-step formation constants of UO_2"2"+-complexes of some N-hydroxysuccinamic acids viz. N-phenyl N-hydroxysuccinamic acid (Rsub(p)H(sub(2))), N-o-toyl N-hydroxysuccinamic acid(Rsub(t)oHsub(2)) and N-m-tolyl N-hydroxysuccinamic acid (Rsub(t)mHsub(2)) have been determined spectrophotometrically. Stabilities are in the ligand order Risup(m)Hsub(2)>Rsub(t)oHsub(2)>Rsub(p)Hsub(2). The first-step hydrolysis constant k' of UO_2"2"+ ion has been determined spectrophotometrically and found to be pk'=4.00 at a constant ionic strength (#mu#=0.5) at 30deg-+0.5deg and the molar extinction coefficients of the species UO_2"2"+ and UO_2(OH)"+ at #LAMBDA#=385 nm are found to be 2.0 and 13.0 respectively. (author).
New dioxouranium (VI) complexes of Schiff bases derived from orthaminophenol and salicylaldehyde, 5,6-benzosalicyladehyde, orthohydroxyacetophenone, orthohydroxybenzophenone, acetoacetanilide and benzoylacetanilide have been prepared and characterized by elemental analysis, conductance, molecular weight, infrared, electronic spectra and magnetic susceptibility measurements. The schiff bases behave as ONO donor tridentate dibasic ligands. Two types of complexes, viz. UO_2L.CH_3OH and UO_2L_2 (where LH_2 schiff base) have been synthesized. The comlexes are monomers, nonelectrolytes and diamagnetic. The #nu#(C=N), #nu#(C-O) (phenolic), #nu#(C-O)(CH_3OH) and the ligands. The #nu#sub(as)(O = U =0) occurs in the range 885-940 cm"-"1 and U-O bond length lies in the 1.72-1.74 A range. The 1:1 complexes are six-cordinated and 1:2 complexes are eight coordinated. (author).
Bioassay-guided fractionation of the EtOH extract of licorice (Glycyrrhiza glabra roots), using a GAL-4-PPAR-g chimera assay method, resulted in the isolation of 39 phenolics, including 10 new compounds (1-10). The structures of the new compounds were determined by analysis of their spectroscopic data. Among the isolated compounds, 5prime-formylglabridin (5), (2R,3R)-3,4prime,7-trihydroxy-3prime-prenylflavane (7), echinatin, (3R)-2prime,3prime,7-trihydroxy-4prime-methoxyisoflavan, kanzonol X, kanzonol W, shinpterocarpin, licoflavanone A, glabrol, shinflavanone, gancaonin L, and glabrone all exhibited significant PPAR-g ligand-binding activity. The activity of these compounds at a sample concentration of 10mg/mL was three times more potent than that of 0.5mM troglitazone.
Several dioxomolybdenum(VI) complexes of the schiff bases derived from salicylaldehyde, 2-hydroxy-1-naphthaldehyde, o-hydroxyacetophenone or pyridoxal and o-aminobenzylalcohol, o-aminophenol, o-hydroxybenzylamine, o-hydroxy(methylbenzyl)amine or 3-amino-2-naphthoic acid have been synthesized and characterized by elemental analysis, electrical conductance, molecular weight, IR and electronic spectral and magnetic susceptibility measurements. The schiff bases behave as dibasic, tridentate ligands and coordinate through ONO donor system forming complexes of the type MoO_2L.X (where LH_2=schiff base, X=H_2O or Ch_3OH). The compounds MoO_2L.Ch_3OH react with 2,2'-dipyridyl to form heterochelates of the type MoO_2L.dipyridyl. The complexes are non-electrolytes, monomers, diamagnetic and possess a cis-MoO_2 structure. The complexes exhibit a ligand-to-metal charge-transfer transition around 25000 cm"-"1. The complexes MoO_2L.X and MoO_2L.dipyridyl are ...
The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh3)2(B)] (where E=P; B=PPh3, py or pip: E=As; B=AsPh3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh3)(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of prim...
The visible absorption spectra of 1,4-(dihydroxy)-9,10-anthraquinone and of Co(II), Ni(II), Cu(II) and Zn(II) chelates have been studied in different organic solvents. This system provides a model for the anthracycline antibiotics and their metal chelates. The band structure of the spectrum has been determined using the second and fourth derivatives of the spectrum. The visible absorption band of the parent molecule can be assigned to a single electronic state with a reduced dipole moment in the excited state; structure in this band is ascribed to two overlapping vibrational progressions. In contrast, the dianion (hydroxy protons removed) shows a single electronic state with an increased dipole moment in the excited state; structure in this band can be assigned to a single vibrational progression. All of the metal chelates show spectra which are similar in appearance to that of the dianion although the identity of the metal determines the bathochromic shift of the absorption band. ...
The endothelin-B (ETB) receptor is a G-protein-coupled receptor that binds endothelin ligands and is essential for the development of epidermal melanocytes and enteric neurons. Recent reports indicate that ETB is localized to nuclei in cardiac ventricular myocytes, although it has been thought that ETB is localized mainly on the plasma membrane. It remains unknown, however, whether this unique distribution of ETB occurs in other tissues. To elucidate the subcellular distribution of ETB in the intestine, we performed immunofluorescence of ETB in mouse intestine using a specific antibody. ETB-like immunoreactivity was detected in both the mucosal and muscle layers. In the mucosal layer, villous epithelial cells, stromal cells of the lamina propria, and cryptic cells were immunostained. Subcellularly, ETB is localized mainly to the nuclei of villous epithelial cells. In the muscle layer, immunoreactivity of ETB was localized to the myenteric plexus. These findings ...
Human complement protein C9 is shown to be a metalloprotein that binds 1 mol of Ca"2"+/mol of C9 with a dissociation constant of 3 #mu#m as measured by equilibrium dialysis. Incubation with EDTA removes the bound calcium, resulting in a apoprotein with decreased thermal stability. This loss in stability leads to aggregation and, therefore, to loss of hemolytic activity upon heating to a few degrees above the physiological temperature. Heat-induced aggregation of apoC9 can be prevented by salts that stabilize proteins according to the Hofmeister series of lyotropic ions, suggesting that the ion in native C9 may ligand with more than one structural element of domain of the protein. Ligand blotting indicates that the calcium binding site is located in the amino-terminal half of the protein. Removal of calcium by inclusion of EDTA in assay mixtures has no effect on the hemolytic activity of C9, and its capacity to bind to C8 in solution, or to ...
Tris(8-quinolinolato)aluminum(III) (Alq3) shows electronic absorption bands at 378, 360 (in a 1:1 mixed solvent of methanol and ethanol (ME) at 77 K), 334, 316, 300, 263, 255.8, and 233 nm in ethanol at room temperature. According to the polarized fluorescence excitation spectrum together with MO calculations, for instance, the 360 nm band is assigned to an LL CT transition (an intramolecular charge transfer transition between two ligands), and the 378 nm band to an LM/ML CT one (an intramolecular charge transfer transition between ligand and metal). Alq3 shows a broad fluorescence band peaking at around 478 nm in the ME matrix at 77 K. The emission spectrum measured with a phosphoroscope has two emission bands at 567 and 478 nm. The 567 nm band accompanies vibronic bands at 578 and 605 nm, being safely assigned to a phosphorescence of Alq3. The lifetimes of the 478 and 567 nm bands are both 5.4 ms. The lifetime of the 478 nm band together with ...
In the MnIII complex of the title compound, [MnIII(C18H12N4O2)(H2O)2]ClO4, the MnIII atom is coordinated by four N atoms from the bpb2- [1,2-bis(pyridine-2-carboxamido)benzene] ligand located in the equatorial plane and two O atoms of water molecules at axial positions, yielding a distorted MnN4O2 octahedral coordination geometry. The bpb2- ligand is nearly planar, with a maximum deviation of 0.2311 (3) A from the mean plane. The MnIII complex cation and the perchlorate anion, both of which are located on twofold rotation axes, are connected by O-H...O and C-H...O hydrogen bonds into a three-dimensional supramolecular network structure.
Crystallography and computer modeling have been used to exploit a previously unexplored channel in the glucocorticoid receptor (GR). Highly potent, nonsteroidal indazole amides showing excellent complementarity to the channel were designed with the assistance of the computational technique AlleGrow. The accuracy of the design process was demonstrated through crystallographic structural determination of the GR ligand-binding domain-agonist complex of the D-prolinamide derivative 11. The utility of the channel was further exemplified through the design of a potent phenylindazole in which structural motifs, seen to interact with the traditional GR ligand pocket, were abandoned and replaced by interactions within the new channel. Occupation of the channel was confirmed with a second GR crystal structure of this truncated D-alaninamide derivative 13. Compound 11 displays properties compatible with development as an intranasal solution formulation, ...
The 1H NMR, electronic absorption, and luminescence spectra, as well as voltammograms of the reduction and oxidation of the complexes [Pd(C?N)(N?N)]ClO4 and [Pd(C?N)(?-OOCCH3)]2 [where (C?N)? is deprotonated 2-phenyl-4,5-dihydro-1,3-oxazole, and N?N is ethylenediamine or 2,2?-bipyridine (bpy)] were compared. Magnetic nonequivalence of protons in the dihydrooxazole ring and upfield shift of the corresponding signals were observed as a result of anisotropic effect of the ring current in palladated phenyl substituents in the [Pd(C?N)(?-OOCCH3)]2 complex having a C 2 symmetry. One-electron reduction wave of [Pd(C?N)bpy]+ was assigned to ligand-centered electron transfer to the ?* orbital of 2,2?-bipyridine, and two oxidation waves of [Pd(C?N)(?-OOCCH3)]2 were attributed to successive one-elect...
Abstract Coordination compounds [Ru(acac)2(Q)] (acac=acetylacetonate; Q=o-benzoquinone) were prepared as complexes 1 (Q=o-benzoquinone), 2 (Q=3-methoxy-o-benzoquinone), 3 (Q=4-methyl-o-benzoquinone), and 4 (Q=3,5-di-tert-butyl-o-benzoquinone). The structures of 1 and 2 were determined to reveal a RuIII/o-benzosemiquinone formulation, supported by analysis of experimental data (spectroscopy, magnetism of 1) and by DFT calculations. The S=1 ground state calculated for 1 stands in contrast to the spin-paired analogues with arylimino-o-benzosemiquinonato and diimino-o-benzoquinone ligands. The close contacts of about 5.3- possible between semiquinone O atoms of different molecules in the crystal allow for intermolecular spin-spin interactions and an overall complex magnetic behavior. One quasi...
Chelating tendencies of several biologically important compounds viz. glycocyamine (GCN: N-amidino-aminoethanoic acid) taurine (TRN: 2-aminoethanesulphonic acid) and pyridoxal [PDL: 3-hydroxy-5-(hydroxymethyl)-2-methyl-pyridine-4-carbaldehyde] have been examined by pH-metric titration technique in their binary complex formation with copper(II) and uranyl(VI) ions. The work has further been extended to investigating the ternary complex formation involving 2.2'-bipyridine. 1,10-phenanthroline or nitrilotriacetic acid as a primary and TRN and PDL as secondary ligands. All the experiments were carried out at 25"0C and at an ionic strength of 0.1M (NaCl0_4) in aqueous or 50% (v/v) aqueous-ethanol medium according to the suitability of the experimental conditions. Stabilities of ternary complexes as compared to those of the corresponding binary complexes of the secondary ligands have also been discussed. (author).
A new cis-dioxomolybdenum complex MoO2(DMLA)2 (DMLA=N,N-dimethyllactamide) has been synthesized and characterized by X-ray crystallography, H NMR and IR spectroscopies and electronic structure calculations at DFT/B3LYP level. This compound (chemical formula C10H20MoO6N2) crystallizes in the orthorhombic space group P212121 with Z=4, a=6.9357(2)?, b=11.8761(4)?, c=17.7251(5), V=1460.00(8)?3 and renders a slightly distorted octahedral structure with two long Mo-O bonds (2.253(3)? and 2.257(3)?) trans to each of the MoO groups and with two short Mo-O bonds of 1.942(3)4? cis to them. The MoO bond length are 1.715(3) and 1.704(3)?). Each lactamide ligand is bidentate; they are coordinated in their deprotonated form with the carbonyl oxygen occupy...
"2"1"1At is one of the most promising radionuclides in #alpha#-radioimmunotherapy (#alpha#-RIT). Unfortunately, biomolecules labeled by direct electrophilic astatination are unstable due to the rapid loss of "2"1"1At under both in vitro and in vivo conditions. The present paper describes the results of our studies on attaching At"- to the rhodium(III) complex with thioether ligand: 1,5,9,13-etrathiacyclohexadecane-3,11-diol (16-S4-diol). Rh"3"+ was chosen as a moderately soft metal cation which should form very strong bonds with soft At"- anions, but first of all because of the kinetic inertness of low spin rhodium(III) d"6 complexes. The 16-S4-diol ligand was selected due to formation of stable complexes with Rh"3"+. The experiments related to optimization of the reaction conditions were performed with the "1"3"1I, basing on a chemical similarity of I"- to At"-. The experiments with "2"1"1At were then carried out under the conditions found ...
In this note it is suggested that binuclear platinum(II) complexes with a solely inorganic bridging pyrophosphito ligand also possess many of the complementary advantages of inorganic and organic dyes. They are evaluated for their potential use as a luminescent solar concentrator material. The disadvantages include: the high cost of platinum; the absorption spectra in solution shows a weaker absorption at 452 nm which may cause reabsorption of emitted light; the positions of the absorption and emission maxima are not at the optimal wavelengths for absorption of sunlight and emission to a solar cell. In spite of these drawbacks the author believes the platinum complexes merit consideration for fabrication of solar concentrator devices.
We demonstrate the rapid optical characterization of large numbers of individual metal nanoparticles freely diffusing in colloidal solution by confocal laser spectroscopy. We find that hollow gold nanospheres and solid silver nanoparticles linked with a bifunctional ligand, both designed nanostructures, exhibit significantly higher monodispersity in their Rayleigh and Raman scattering response than randomly aggregated gold and silver nanoparticles. We show that measurements of rotational diffusion timescales allow sizing of particles significantly more reliably than can be obtained using translational diffusion timescales.
Single-crystalline CeRh_2Si_2 and CePd_2Si_2 were grown by the Czochralsky pulling method and the temperature dependence of magnetic susceptibility was investigated. The crystalline electric field (CEF) states in each compound were determined by considering the tetragonal CEF Hamiltonian with mean-field approximation. Interactions between Ce"3"+ ion and the surrounding ligands in CeRh_2Si_2 turned out to be strong and highly anisotropic in comparison to CePd_2Si_2. (orig.)
Several new complexes of isomeric schiff bases derived from salicylaldehyde and o-hydroxybenzylamine/o-aminobenzyl-alcohol with Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), and Dy(III) have been synthesized and characterized by elemental analysis, molar conductance, IR, electronic spectra and magnetic susceptibility measurements. The schiff bases behave as monobasic tridentate ONO donor and dibasic tridentate ONO donor ligands and form complexes of the type Ln(LH)L. (author). 12 refs.
The maintenance of a balance between cell gain and cell loss is essential for proper liver function. The exact role of aryl hydrocarbon receptor (AhR) in regulating cell proliferation and apoptosis of liver cells remains unclear, since ligand-dependent activation of AhR has been shown to induce cell cycle arrest, proliferation, differentiation or apoptosis, depending on the cellular model used. AhR can directly interact with retinoblastoma protein in hepatic cells, forming protein complexes that can efficiently block cell cycle progression by inducing G1 arrest, or to induce the expression of inhibitors of cyclin-dependent kinases, such as p271. On the other hand, it has been suggested that AhR could play a stimulatory role in cell proliferation, either directly or by mediating a release from contact inhibition. It is now generally accepted that progenitor cells exist in the liver, are activated in various liver diseases and can form a potential target cell ...
Transformed Drosophila Kc cell lines, resistant to methotrexate, an inhibitor of de novo purine and pyrimidine synthesis, have been obtained by calcium phosphate transfection of plasmids containing...Full Text Available
Replication of plus-strand RNA viruses depends on host factors that are recruited into viral replicase complexes. Previous studies showed that eukaryotic translation elongation factor (eEF1A) is one...Full Text Available
We describe a novel 13C enriched precursor molecule, sodium 1-13C acetylenedicarboxylate, which after hydrogenation by PASADE-NA (Parahydrogen and Synthesis Allows Dramatically...Full Text Available
Electricity generation from natural gas in gas turbine units can be made substantially more efficient by preliminary methane conversion to a synthesis gas containing hydrogen and carbon monoxide and/or by the use of some of the synthesis gas produced in industry. An alternative improvement involves the introduction of solid oxide fuel cells (SOFCs) and the use of the synthesis gas in them. In this study, a modified scheme of gas turbine cycle that includes an SOFC, a membrane reactor (instead of a traditional combustion chamber), and a catalytic reactor to perform methane conversion to produce hydrogen (synthesis gas) is proposed. Variations of the energy and exergy efficiencies of the integrated system with operating conditions are provided, showing, for example, that SOFC efficiency is enhanced if the fuel cell active area is augmented. The SOFC stack efficiency can be maximized by reducing the steam ...
Previous work has provided evidence that plants may require boron to maintain adequate levels of pyrimidine nucleotides, suggesting that the state of boron deficiency may actually be one of pyrimidine...Full Text Available
Deuterated lipoxygenase and cyclooxygenase derivatives of eicosatetraenoic acid (arachidonic acid) and their metabolites are indispensable tools for organic trace analysis, biomedical studies, and mechanistic investigations on the corresponding endogenous (unlabelled) eicosanoids. Methods for the preparation of deuterated eicosanoids are reviewed.
A method was developed to synthesize /sup 14/C-labelled n-alkanes for use in cigarette smoke studies. Specifically, n-(18-/sup 14/C)-octatriacontane was synthesized from 1 mCi (1-/sup 14/C)stearic acid in a radiochemical yield of 20%. The key features of this synthesis were two consecutive alkylations of tosylmethyl isocyanide followed by acid hydrolysis to (18-/sup 14/C)-19-octatriacontanone and modified Wolff-Kishner reduction to the n-alkane. After purification on silica gel 25 mg of (18-/sup 14/C)octatriacontane was obtained with a total radioactivity of 200 ..mu..Ci, a specific activity of 4.3 mCi/mmol, and a radiochemical purity in excess of 98% by thin layer radiochromatography. The method has also been applied to the synthesis of unlabeled n-pentatriacontane and is considered to be generally applicable to the synthesis of radiolabeled alkanes from radiolabeled fatty acids.
In many dinoflagellate species, the plastid genome has been proposed to exist as a limited number of single-gene minicircles, and many genes normally found in the plastid genome are nuclear-encoded....Full Text Available
We have synthesized a novel stable precursor, saligenin phosphorotrichloridate, which, on reaction with N-monobiotinyldiamines, generates a series of biotinylated covalent inhibitors of serine esterases....Full Text Available
The purpose of this study was to synthesize biocompatible polyvinylpyrrolidone (PVP)-coated iron oxide (PVP-IO) nanoparticles and to evaluate their efficacy as a magnetic resonance imaging (MRI)...Full Text Available
The objective of this research was to determine the role of acidic ribosomal protein (ARP) phosphorylation in translation. Ribosomes (Rbs) from germinated maize (Zea mays L.) axes had...Full Text Available
The changes in protein species synthesized during early Drosophila embryogenesis were characterized by two-dimensional electrophoresis. Of the 261 proteins scored, 68 (26%) show dramatic changes in...Full Text Available
Performance on serial tasks is influenced by first- and higher-order sequential effects, respectively due to the immediately previous and earlier trials. As response-to-stimulus interval (RSI)...Full Text Available
Interleukin 12 (IL-12) activates natural killer (NK) and T cells with the secondary synthesis and release of interferon-gamma (IFN-gamma) and other cytokines. IL-12-induced organ alterations are reported...Full Text Available
In vitro translation systems were prepared with supernatant factors from wheat germ and 80S ribosomes from wheat germ, barley embryos, watermelon cotyledons, pea cotyledons, and castor...Full Text Available
Carbon nanotubes (CNTs) are considered one of the most promising materials in nanotechnology, with attractive properties for many technologic applications. The different synthesis, purification, and...Full Text Available
Hyaluronan (HA) is important for joint cavitation, lubrication, volume regulation and synovial fluid drainage but little is known about the regulation of joint HA synthesis/secretion in vivo....Full Text Available
BackgroundGlucocorticoids down-regulate cytokine synthesis and suppress inflammatory responses. The glucocorticoid receptor (GR) antagonist RU486 may exacerbate the inflammatory...Full Text Available
SummaryThe numerous applications of hydrogelators have led to rapid expansion of this field. In the present work we report the facile synthesis of amphiphilic hydrogelators having a quaternary...Full Text Available
Increased intrauterine prostaglandin (PG) production is crucial for the initiation of parturition. To investigate the mechanisms controlling intrauterine PG synthesis, we examined the expression of...Full Text Available
Strong aqueous ammonium hydroxide used to remove N-acyl protecting groups from synthetic oligoribonucleotides causes removal of some alkylsilyl protecting groups from 2'-hydroxyls and leads to chain...Full Text Available
The high-yield, stereoselective conversion of geraniol (3,7-dimethyl-trans-2,6-octadien-1-ol) to the insect juvenile hormone, methyl 12,14-dihomojuvenate (methyl cis-10-epoxy-3,11-dimethyl-7-ethyl-trans,...Full Text Available
The conversion of coal to oil can be carried out in two ways. A synthesis route and a degradation route. Each of these routes are described and several degradation processes are explored. The testing of several fuels produced from coal is also given considerations.
The in vitro response of melatonin synthesis was assessed by incubation of individual whole pineal glands for 4 hr without or with different concentrations of isoproterenol in the medium. Pineals were taken either at the end of the 14-hr light phase (day)...
Nucleoside 3'-phosphoramidite and chlorophosphite reagents have been found to react with the lactam function of guanine. This reaction caused unsatisfactory results when oligodeoxyribonucleotides containing...Full Text Available
The synthesis and degradation of anthropogenic and natural organohalides are the basis of a global halogen cycle. Chlorinated hydroquinone metabolites (CHMs) synthesized by basidiomycete fungi and present...Full Text Available
Salamanders regenerate their appendages after amputation and nerves are required for this process. Experiments were designed to test the idea that one way nerves could affect blastema cell proliferation is by influencing the metabolism of extracellular matrix (ECM) components and to identify neurotrophic factors which promote blastema cell mitosis. Temporal and spatial differences of glycosaminoglycans (GAGs) synthesis is innervated and denervated limbs were examined. Hyaluronic acid (HA) was found to be the major GAG produced during the proliferative period and chondroitin sulfate during differentiation. Denervation reduced synthesis of both these components by half. Dorsal root ganglia and fibroblast growth factor (FGF), a brain-derived mitogen, similarly doubled GAG synthesis in cultured blastemas, the FGF-effect being primarily on HA production. Histochemical and autoradiographical results confirmed the biochemical ...
Acylation stimulating protein (ASP, C3adesArg) is an adipose tissue derived hormone that stimulates triglyceride (TG) synthesis. ASP stimulates lipoprotein lipase (LPL) activity by relieving feedback...Full Text Available
In the past, the fermentation activity of Saccharomyces cerevisiae in substrates with a high concentration of sucrose (HSuc), such as sweet bread doughs, has been linked inversely to invertase activity...Full Text Available
Unless relaxation of the stringent response is achieved, all nongrowing bacteria rapidly develop resistance to autolysis induced by a variety of agents, including all classes of cell wall synthesis...Full Text Available
A mutation in a new gene, molR, prevented the synthesis in Escherichia coli of molybdoenzymes, including the two formate dehydrogenase isoenzymes, nitrate reductase and trimethylamine-N-oxide reductase....Full Text Available
The authors investigate the possibility of the direct heterogeneous catalytic synthesis of ethylbenzoate from benzonitrile. The catalysts tested were oxides of aluminium, titanium, and vanadium. The main conversion product detected chromatographically was ethylbenzoate; benzaldehyde, benzamide, and benzanilide were also identified. Aluminium oxide was found to be the most effective catalyst.
Though the genetic background of ischaemic and haemorrhagic stroke is often polygenetic or multifactorial, it can in some cases result from a monogenic disease, particularly in young adults. Besides...Full Text Available
Hepatitis delta virus (HDV) contains a viroid-like circular RNA that replicates via a double rolling circle replication mechanism. It is generally assumed that HDV RNA is synthesized and remains exclusively...Full Text Available
In the synthesis of the peptidyl-polymer corresponding to the sequence (57-100) of the ..beta.. chain of human hemoglobin on Teflon with radiationally grafted polystyrene a comparative study was made of different methods of fragment condensation. It was shown that the most effective methods are azide condensation and condensation with the use of complex F.
In the synthesis of the peptidyl-polymer corresponding to the sequence (57-100) of the #beta# chain of human hemoglobin on Teflon with radiationally grafted polystyrene a comparative study was made of different methods of fragment condensation. It was shown that the most effective methods are azide condensation and condensation with the use of complex F.
... of Viscous Liquids, Glasses, and Crystalline Materials Under Extremes of Pressure and Temperature ... Materials 9624724 ENG AZ U of Arizona Gervay Jacquelyn Synthesis of Novel Materials Utilizing Sialic ...
The results of a study of the expression of embryonic hemoglobin genes in mice which show an imbalance of alpha and non-alpha chain synthesis are reported. (ACR)
Lumbricus terrestris (Annelid, Oligocheta) is capable of cellular- and humoral-specific reactions against natural antigens. Is this earthworm able to elaborate a response of antibody type against a...Full Text Available
Clostridium perfringens type A food poisoning is the second most commonly identified bacterial food-borne illness. Sporulation contributes to this disease in two ways: (i) most food-poisoning...Full Text Available
AIM: To analyze the antiviral mechanism of Epigallocatechin gallate (EGCG) against hepatitis B virus (HBV) replication.METHODS: In this research, the HBV-replicating cell line HepG2.117 was used...Full Text Available
Isolated cauliflower (Brassica oleracea) bud plastids, purified by isopycnic centrifugation in density gradients of Percoll, were found to be highly intact, to be practically devoid...Full Text Available
Glutathione (GSH) depletion sensitizes human lung carcinoma (A549-T27) cells to the cytotoxic effects of Cd++. The effects of GSH depletion on Cd++ accumulation and Cd++-induced metallothionein (MT) content were investigated to determine the possible role of these Cd++ responses in the sensitization process. Cellular GSH was depleted to 20% to 25% of control levels with buthionine sulfoximine (BSO), or diethyl maleate (DEM), respectively. Neither treatment significantly affected Cd++-induced accumulation of exogenous 35s-cysteine into intracellular MT in a dose-dependent fashion. The results indicate that neither enhanced Cd++ accumulation nor reduced MT synthesis plays a primary role in affecting enhanced Cd++ cytotoxicity in A549 cells with reduced GSH levels. Although BSO inhibition of GSH synthesis enhanced MT synthesis, it sensitized the cells to Cd++, which suggests an additive effect of GSH and MT in cadmium ...
The notes describe in detail primary and secondary galvanic cells, fuel cells, electrochemical synthesis and electroplating processes, corrosion: measurments, inhibitors, cathodic and anodic protection, details of metal dissolution reactions, Pourbaix diagrams and purification of waste water from galvanic industries.
Proline accumulation in NaCl-treated excised barley (Hordeum vulgare var Larker) leaves was studied. Leaves were treated by placing the cut end in NaCl solutions and allowing the salt...Full Text Available
Mice lacking acyl-CoA:diacylglycerol acyltransferase 1 (DGAT1), an enzyme that catalyzes the terminal step in triacylglycerol synthesis, have enhanced insulin sensitivity and are protected from...Full Text Available
The effects of temperature on rates of cellulose synthesis, respiration, and long-term glucose uptake were investigated using cultured cotton ovules (Gossypium hirsutum L. cv Acala...Full Text Available
The effect of plant water deficit on ethylene production by intact plants was tested in three species, beans (Phaseolus vulgaris L.), cotton (Gossypium hirsutum L.)...Full Text Available
The liver plays a vital role in glucose homeostasis, the synthesis of bile acids and the detoxification of foreign substances. Liver culture systems are widely used to test adverse effects of drugs...Full Text Available
The syntheses and applications of two metallointercalators, Rh(bpy)2(chrysi)3+ and Rh(bpy)2(phzi)3+, that target single base mismatches in DNA are...Full Text Available
Recently reported technologies for DNA-directed organic synthesis and for DNA computing rely on routing DNA populations through complex networks. The reduction of these ideas to practice has been limited...Full Text Available
CF-23“The biggest stumbling block for biological sciences turned out to be synthetic organic chemistry” – Elias A. Zerhouni, Former NIH Director in Chemical...Full Text Available
ATP-binding cassette A3 (ABCA3) is a lipid transport protein required for synthesis and storage of pulmonary surfactant in type II cells in the alveoli. Abca3 was conditionally deleted...Full Text Available
BackgroundWax esters are important ingredients in cosmetics, pharmaceuticals, lubricants and other chemical industries due to their excellent wetting property. Since the naturally...Full Text Available
BackgroundStructured noncoding RNAs perform many functions that are essential for protein synthesis, RNA processing, and gene regulation. Structured RNAs can be detected by comparative...Full Text Available
A balanced application of chemiosmosis to plant mitochondria is presented. Electron transport carriers are sequenced to achieve proton translocation across the inner membrane. The processes of proton translocation, use, and release are integrated to yield a description of the effective proton gradient available for metabolite transport and ATP synthesis. 27 references, 6 figures.
The synthesis of an extracellular ribbon of cellulose in the bacterium Acetobacter xylinum takes place from linearly arranged, membrane-localized, cellulose-synthesizing and extrusion complexes that...Full Text Available
Zinc modulates the activity of glutamic acid decarboxylase, the rate limiting enzyme in the synthesis of gamma-aminobutyric acid (GABA), which is a major inhibitory neurotransmitter. Low cerebrospinal...Full Text Available
The overall goal of the Gas-to-Liquids Program at the U.S. Department of Energy`s Pittsburgh Energy Technology Center (PETC) is to develop technologies for the production of hydrocarbon fuels and premium chemicals from light alkane gases. PETC`s current Gas-to-Liquids Program comprises the development of four primary advanced conversion technologies, namely, partial oxidation, oxidative coupling, oxyhydrochlorination, and novel conversion processes. Based on the current state of development, it can be concluded that, in the near future, one or more of these technologies will reach proof-of-concept demonstration. Oxyhydrochlorination is the most advanced direct conversion technology, and the synthesis of lower cost methyl chloride from natural gas would impact several commercial technologies that utilize methyl chloride as an intermediate to high value products. Technology development for the partial oxidation of methane to synthesis gas using ...
Thaxtomin A is a phytotoxin produced by Streptomyces scabies and other Streptomyces species, the causative agents of common scab disease in potato and other taproot...Full Text Available
We recently reported that human immunodeficiency virus type 1 (HIV-1) unintegrated linear DNA displays a discontinuity in its plus strand, precisely defined by a second copy of the polypurine tract...Full Text Available
A cDNA encoding a cytochrome P450 enzyme was isolated from a cDNA library of the corpora allata (CA) from reproductively active Diploptera punctata cockroaches. This P450 from the endocrine...Full Text Available
Synthetic complementary oligonucleotides are useful hybridization probes for the detection of mRNAs and genes encoding proteins for which only a partial amino acid sequence is known. Usually this involves...Full Text Available
May 31, 2011 ... Synthesis and Structural Characterization of a Novel Indium Mercapto Derivative [Clln(SCH2(CO)O)2]2-[(4-MepyH)2]2+. 284. System Mass ...
Amino acids other than those that serve as ligands have been found to influence the chemical properties of transferrin iron. The catalytic ability of pyrophosphate to mediate transferrin iron release to a terminal acceptor is largely quenched by modification non-liganded histine groups on the protein. The first order rate constants of iron release for several partially histidine modified protein samples were measured. A statistical method was employed to establish that one non-liganded histidine per metal binding domain was responsible for the reduction in rate constant. These results imply that the iron mediated chelator, pyrophosphate, binds directly to a histidine residue on the protein during the iron release process. EPR spectroscopic results are consistent with this interpretation. Kinetic and amino acid sequence studies of ovotransferrin and lactoferrin, in addition to human serum transferrin, have allowed the ...
Derivatives of angiotensin with a sarcosine substitution at the carboxy terminus and an aliphatic amino acid substitution at the amino terminus have been shown to be competitive ligands for the angiotensin receptor. Scatchard plots derived from saturation isotherm data in bovine adrenal particulates consistently demonstrate three to five times the number of binding sites for "1"2"5I-Sarl,Ile8-AII ("1"2"5I-SI-AII) than for "1"2"5I-AII in experiments in which the two ligands are run side-by-side. A significant difference between "1"2"5I-AII and "1"2"5I-SI-AII binding to detergent solubilized angiotensin receptors was observed. Of the "1"2"5I-AII binding sites, about 85-90% were recovered upon solubilization. In contrast, the recovery of "1"2"5I-SI-AII binding sites was only 4-5%. To determine whether binding sites labeled in the soluble state represent biologically significant AII receptors, they examined the ability of selected angiotensin ...
A way to synthesize the transient zwitterionic silylene L'Si: 8 {L'=CH[(C=CH(2))CMe(N(tBu))(2)]} and achieve its facile dimerization to the remarkable N-heterobicyclic disilane 8(2) is described. At first, employing the beta-diketiminate ligand L [L=CH(CMeN(tBu))(2)], both starting materials LH (2) and its N-lithium salt LLi (3) can react with SiBr(4) to yield the silylene precursor L'SiBr(2) (4) by silicon-induced C-H activation at an exocyclic methyl group on the backbone of the ligand. Compound 4 reacts with SiBr(4) above room temperature to afford the unexpected terminal CH(SiBr(3))-substituted dibromosilane 6 along with the unique tricyclic trisilane 7. Reduction of 4 with KC(8) at 0 degrees C furnishes the novel N-heterobicyclic disilane 8(2), which is a formal dimer of the desired zwitterionic silylene L'Si: (8). It has been reasoned that compound 8(2) may results from [4+1] cycloaddition of two molecules of 8 to give the transient dimer ...
The research has involved the characterization of catalyst acidity, [sup 2]D NMR studies of Bronsted acid sites, and kinetic, calorimetric, and spectroscopic studies of methylamine synthesis and related reactions over acid catalysts. Approach of this work was to explore quantitative correlations between factors that control the generation, type, strength, and catalytic properties of acid sites on zeolite catalysts. Microcalorimetry, thermogravimetric analysis, IR spectroscopy, and NMR spectroscopy have provided information about the nature and strength of acid sites in zeolites. This was vital in understanding the catalytic cycles involved in methylamine synthesis and related reactions over zeolite catalysts.
This report presents the main conclusions of 15 years of researches managed by the CEA. This report is the preliminary version of the 2005 final report. It presents the main conclusions of the actions on the axis 1 and 3 of the law of the 30 December 1991. The synthesis report on the axis 1 concerns results obtained on the long lived radionuclides separation and transmutation in high level and long lived radioactive wastes. the synthesis report on the axis 3 presents results obtained by the processes of conditioning and of ground and underground long term storage. (A.L.B.)
Several enzymes of the metabolic pathways responsible for metabolism of cytosolic ribonucleotides and deoxyribonucleotides are located in mitochondria. Studies described in this paper suggest dysfunction of the mitochondria to affect these metabolic pathways and limit the available levels of cytosolic ribonucleotides and deoxyribonucleotides, which in turn can result in aberrant RNA and DNA synthesis. Mitochondrial dysfunction has been linked to genomic instability, and it is possible that the limiting effect of mitochondrial dysfunction on the levels of nucleotides and resulting aberrant RNA and DNA synthesis in part can be responsible for this link. This paper summarizes the parts of the metabolic pathways responsible for nucleotide metabolism that can be affected by mitochondrial dysfunction.
A procedure for high level tritium labelling at the C2-H position of adenosine 5`-triphosphate ([2-{sup 3}H]-ATP, 1), based on the tritiodehalogenation reaction of 2-bromoadenosine 5`-triphosphate (2) has been elaborated. This precursor was prepared in a six-step synthesis from guanosine. The tritiodehalogenation of (2) for three hours over palladium oxide in phosphate buffer yielded tritium labelled ATP with high specific activity, in good chemical yield. (author).
The synthesis and structural characterization of a novel In(III) complex is described. The reaction between InCl3 with sodium mercapto-acetic acid, (NaSCH2(CO)OH) in 4-methylpyridine, (CH3(C5H5N), (4-Mepy)) at 25 C affords (ClIn(SCH2(CO)O)2)2- ((4-MepyH)2...
The synthesis and biophysical characterization of four prodrug ether phospholipid conjugates are described. The lipids are prepared from the anticancer drug chlorambucil and have C16 and C18 ether chains with phosphatidylcholine or phosphatidylglycerol headgroups. All four prodrugs have the ability to form unilamellar liposomes (86-125 nm) and are hydrolyzed by phospholipase A2, resulting in chlorambucil release. Liposomal formulations of prodrug lipids displayed cytotoxicity toward HT-29, MT-3, and ES-2 cancer cell lines in the presence of phospholipase A2, with IC50 values in the 8-36 ?M range.
The purpose of this study is fabrication and characterization of silver nanofluid by the submerged arc nanoparticle synthesis system (SANSS). The silver metal electrodes under the electrical discharge will melt and evaporate rapidly and condense to form the nanoparticles in the lower temperature dielectric liquid and produce the suspended nanoparticle. The results showed that the spherical nanosilver particle formed in the ethylene glycol and the mean particle size is about 12.5 nm. The prepared silver nanofluid was irradiated under the 410 nm visible light, electrons could be excited from the valence band to the conduction band. The silver nanofluid more closely resembles Newtonian fluids.
The Eighth Indirect Liquefaction Contractors' Review Meeting was held November 15-17, 1988 at the Pittsburgh Hyatt Hotel. Twenty-eight presentations were made by contractors, invited speakers, and Pittsburgh Energy Technology Center R and D personnel. Six areas of research were covered: synthesis gas conversion to oxygenates; light hydrocarbon gas conversion; slurry reactor hydrodynamics; production, clean-up and conversion to hydrocarbon fuels; Fischer-Tropsch products upgrading; and, synthesis gas bioconversion. The meetings also included a panel discussion on direct methane conversion research. Individual projects are processed separately for the data bases.
An improved method for the synthesis of (/sup 15/N) 16-Doxyl stearate, a fatty-acid spin label, is reported. The method requires only one mole of (/sup 15/N) 2-amino-2-methyl propanol per mole of methyl keto stearate with an overall yield of about 50%. In contrast, the previous method produced only 1-3% yield. The great improvement in yield was achieved mainly through the reduction of reaction volume which increases the reaction rate by the law of mass action.
The effect of protein malnutrition on the metabolism of collagen in bone was studied in young female albino rats after a single injection of "3H-proline. Both specific and total radioactivities of hydroxyproline in the total collagen of the bone were found to decrease in the protein-deficient animals, indicating decreased rate of collagen synthesis. In the urine the amount of hydroxyproline excreted and total radioactivity of "3H-hydroxyproline were greatly decreased. The results of the present investigation therefore clearly indicate decreased synthesis and catabolism of collagen in bones of protein deficient animals compared to controls. (auth.).
The objective of this contract is to research, develop and demonstrate a novel ceramic membrane reactor system for the low-cost conversion of natural gas to synthesis gas and hydrogen for liquid transportation fuels: the ITM Syngas process. Through an eight-year, three-phase program, the technology will be developed and scaled up to obtain the technical, engineering, operating and economic data necessary for the final step to full commercialization of the Gas-to-Liquids (GTL) conversion technology. This report is a summary of activities through February 1999.
The objective of this contract is to research, develop and demonstrate a novel ceramic membrane reactor system for the low-cost conversion of natural gas to synthesis gas and hydrogen for liquid transportation fuels: the ITM Syngas process. Through an eight-year, three-phase program, the technology will be developed and scaled up to obtain the technical, engineering, operating and economic data necessary for the final step to full commercialization of the Gas-to-Liquids (GTL) conversion technology. This report is a summary of activities through September 1999.
One-pot multi-component condensation of benzyl, aldehydes, ammonium acetate and primary amines were used for synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted-1H-imidazole derivatives under MW radiation using amberlyst A-15 as a catalysts. This catalyst has several advantages (simple work-up, low cost and reusability).
Biosynthesis of hemoglobin and some of its electrophoretic fractions in red cells of peripheral blood and spleen of irradiated (650 R) rats has been studied. Hemoglobin synthesis is found to be most drastically inhibited in the first and second fractions on the first and eighth days after irradiation and in the fifth and sixth fractions on the eighth day (less expressed). The synthesis is restored on the twelfth day, the process under study proceeding more slowly in the above-mentioned fractions than in others. In the course of radiation sickness, the biosynthesis of certain hemoglobin fractions varies differently in the hemoglobin-synthesizing cells of peripheral blood than in the cells of spleenic erythroid series.
The liquid-phase synthesis of metal oxide nanoparticles in organic solvents under exclusion of water is nowadays a well-established alternative to aqueous sol-gel chemistry. In this article, we highlight some of the advantages of these routes based on selected examples. The first part reviews some recent developments in the synthesis of ternary metal oxide nanoparticles by surfactant-free nonaqueous sol-gel routes, followed by the discussion of the morphology-controlled synthesis of lanthanum hydroxide nanoparticles, and the presentation of structural peculiarities of manganese oxide nanoparticles with an ordered Mn vacancy superstructure. These examples show that nonaqueous systems, on the one hand, allow the preparation of compositionally complex oxides, and, on the other hand, make use of the organic components (initially present or formed in situ) in the reaction mixture to tailor the morphology. Furthermore, obviously ...
Novel ligands cis-2,6-bis[N,N-bis(carboxymethyl)aminomethyl]-1-piperidineacetic acid (PIP-DTPA), cis-[(1R,11S)-6,9,15-Tris-carboxymethyl-3,6,9,15-tetraazabicyclo[9.3.1] pentadec-3-yl]-acetic acid (PIP-DOTA), cis-{l_brace}2,7-bis-[bis-carboxymethyl-amino)-methyl]-azepan-1-yl{r_brace}-acetic acid (AZEP-DTPA), [2-(4,7-bis-carboxymethyl-[1,4,7]triazacyclononan-1-yl-ethyl] -2-carbonylmethyl-amino]-tetraacetic acid (NETA) and [{l_brace}4-carboxymethyl-7-[2-(carboxymethylamino)-ethyl]-perhydro-1,4,7-triazonin-1-yl{r_brace}-acetic acid (NPTA) are investigated as potential chelators of {sup 177}Lu, {sup 9}Y, {sup 212}Pb and {sup 213}Bi for radioimmunotherapy (RIT). The new ligands are radiolabeled with {sup 177}Lu, {sup 86/88/9}Y, {sup 203}Pb and {sup 205/6}Bi, and in vitro stability and in vivo stability of the radiolabeled complexes are assessed in human serum and athymic mice, respectively. In vitro studies indicate that all radiolabeled complexes ...
Increasing photosynthesis rate by raising CO{sub 2} and lowering O{sub 2} usually results in measured rates lower than those expected from the kinetics of rubisco. The failure of leaves to utilize the increased efficiency of rubisco has been attributed to limitations in rates of either starch or sucrose synthesis, which lead to a lowering of Pi and a reduction in the rate of ATP synthesis. In sugar beet leaves, increasing CO{sub 2} from 350 to 600 {mu}L L{sup {minus}1} usually increased photosynthesis only about 10%, compared to the 45% expected, and lowering O{sub 2} from 2 to 21% increased photosynthesis only an additional 20%, compared to the additional 40% expected. In some cases, raising CO{sub 2} increased photosynthesis the full 30% with no further increase occurring upon lowering O{sub 2}. In all cases, rates of starch and sucrose synthesis consistently increased in proportion to increasing photosynthesis rate. ...
Prostaglandin E2 (PGE2) has been shown to increase the synthesis of hyaluronic acid in cultured fibroblasts by increasing the activity of hyaluronate synthetase, a group of plasma membrane-bound synthetic enzymes. We examined whether PGE2 also increased the activity of those enzyme systems involved in the synthesis of sulfated glycosaminoglycan in the human embryonic lung fibroblast. Exposure of cells to PGE2 resulted in dose-dependent increases in glucosamine incorporation into all sulfated glycosaminoglycan subtypes. PGE2 at 10(-7) mol/L increased total glycosaminoglycan per dish to 21.6 +/- 3.1 micrograms versus 12.0 +/- 2.5 micrograms in control untreated cultures. Stimulation of endogenous PGE2 production by bradykinin had a similar effect on glycosaminoglycan synthesis. To examine whether PGE2 affected sulfated glycosaminoglycan protein core production, cells were labeled with tritiated glucosamine in the presence of ...
Hydrocarbon synthesis during CO hydrogenation over Pd/M-ZSM5 (M=H,Na,La) and Pd/SiO/sub 2/ has been investigated. Overall activity depended on the cation-exchanged form of the support and decreased in the order Pd/La-ZSM5 = Pd/Na-ZSM5 > Pd/H-ZSM5 > Pd/SiO/sub 2/. The zeolite-supported catalysts showed high selectivity towards saturated C/sub 2/-C/sub 6/ hydrocarbons, whereas Pd/SiO/sub 2/ favored methanol production. Increasing temperature and H/sub 2//CO feed ratio led to higher reaction rates, lower yields of C/sub 2/-C/sub 6/ products, and increased lighter hydrocarbons. A mechanical mixture of Pd/SiO/sub 2/ and Na-ZSM5 showed similar product distribution as Pd/Na-ZSM5. Infrared spectra of the catalysts under reaction conditions indicate the presence of adsorbed oxygenates on the zeolite. Changes in the IR bands during the initial stages of the reaction suggest that surface species on the zeolite are not methanol synthesis ...
Conversion of coal gas into liquid products is a multistep process which involves numerous unit processes. Compared with similar processes using natural gas as feedstock, there are challenges, particularly with the gas purification. There are, however, also advantages when using a carbon-monoxide-rich gas which ultimately may result in a greatly simplified process. This paper discusses the challenges when converting a gas from an entrained coal gasifier into a liquid product and the paper presents the various options available. The following issues will be touched upon: sour gas shift and adjustment of the H{sub 2}/CO ratio; acid Gas Removal (AGR) - when and how; syngas purification; methanol and combined methanol/DME synthesis; gasoline synthesis; future integrated processes. Here, various options are available depending on the gasifier; not only dry or slurry feed but also the question of quench as well as the selected scrubbing temperature ...
The processes of lung growth, injury, and repair are characterized by alterations in fibroblast synthesis and interstitial distribution of extracellular matrix components. Transforming growth factor beta (TGF-beta), which is postulated to play a role in modulating lung repair, alters the distribution of several matrix components such as collagen and fibronectin. We studied the effect of TGF-beta on the synthesis and distribution of the various glycosaminoglycans (GAGs) and whether these effects may explain its role in lung repair. Human diploid lung fibroblasts (IMR-90) were exposed to various concentrations of TGF-beta (0-5 nM) for variable periods of time (0-18 h). Newly synthesized GAGs were labeled with either (3H)glucosamine or (35S)sulfate. Individual GAGs were separated by size exclusion chromatography after serial enzymatic and chemical digestions and quantitated using scintillation counting. There was a dose-dependent increase in total ...
Perylene bisimides (PBIs) represent an important class of organic n-type semiconductors exhibiting a relatively high electron affinity among large-band-gap materials. Herein synthesis and characterization of several unsymmetrical N-substituted PBI dyes is presented and the thermotropic behavior, which is strongly affected by the respective N-substituents was investigated. Two different series of highly soluble and fluorescent derivatives have been synthesized: (1) PBIs bearing swallow-tailed alkyl chains, different in size or (2) one swallow-tailed alkyl chain and one branched oligoethylenglycolether. Synthesis of these PBIs is generally feasible by two distinct divergent synthesis approaches. Thermotropic behavior was studied by DSC, POM and XRD measurements. Inherent {pi}-{pi} interactions between cofacially orientated perylene molecules and the elliptic shape of the molecule favor the ordering in columns and ...
The synthesis of ["1"1C]phenobarbital, ["1"1C]pentobarbital and["1"1C]amobarbital labelled in the 5-[1-"1"1C]ethyl position is reported. The malonic esters R- CH(CO_2Et)_2 [R phenyl-, 1-methylbutyl-, and 3- methylbutyl- were alkylated with [1-"1"1C]ethyl iodide prepared from ["1"1C]carbon dioxide. Ring closure of the 2-[1-"1"1C]ethyl-labelled malonic esters with urea afforded 5-[1-"1"1C]ethyl-phenobarbital,-phenobarbital, -pentobarbital and -amobarbital synthesis times of 42-47 min, counted from ["1"1C] carbon dioxide. In typical syntheses starting with 3 GBq pentobarbitol and (81 mCi) ["1"1C]carbon dioxide, 150-215 MBq (4-6 mCi) were produced in 25-30% decay corrected -amobarbital radiochemical yields with radiochemical purities greater than 98%. (author).
Following tuber excision from the mother plant sucrose synthase activity fell from 3,120 to 960 nmol/g.f. wt./h within 7 days and starch synthesis ({sup 14}C sucrose incorporated into isolated discs) from 23 to 7 nmol/g.f. wt./h. While the maximum catalytic activity of sucrose synthase was more than sufficient to account for the observed rate of starch synthesis a maximum of 27% of sucrose incorporated by discs was converted into starch within 3 h. This compared with 80% conversion of {sup 14}C glucose incorporated. Tuber excision also reduced the rate of starch biosynthesis with glucose as a substrate (from 206 to 64 nmol/g.f. wt./h). The activities of UDPG-pyrophosphorylase, PPi-PFK, ATP-PFK, starch synthase and hexokinase (glucose or fructose substrates) were unaffected by tuber removal. ADPG pyrophosphorylase activity was reduced from 8,000 to 4,500 nmol/g.f. wt./h. Preliminary experiments indicate that the decline in sucrose synthease ...
The usefulness of psychoanalysis to psychosomatic medicine has been limited by the longstanding assumption that the psychological disorder in psychosomatic patients resembles the conflict-based psychopathology that Freud identified in psychoneurotic patients. Recent investigations of the alexithymia construct, and the discovery that social relationships can influence health over the entire life span, have challenged this assumption and created an opportunity for a new and active involvement of psychoanalysis with psychosomatic medicine. In this contribution, I offer a synthesis of contemporary psychoanalytic observations and theories with concepts and research findings from developmental psychology, developmental biology, and the biomedical sciences. The proposed synthesis is consistent with the view that living organisms are self-regulating cybernetic systems; it also extends an evolving new psychosomatic model that conceptualizes illnesses ...
The production of radiopharmaceuticals used in positron emission tomography (PET) can require large amounts of activity at the start of synthesis in order to yield sufficient labeled material for clinical studies. Several investigators have developed remote and automated systems for the routine production of PET radiopharmaceuticals in order to reduce radiation exposure to personnel. Such devices, however, suffer from limited flexibility and can be relatively complicated in design. These systems are also limited to the production of a single or a few closely related compounds. Furthermore, changes in chemistry would require considerable modifications in hardware and/or software in order to bring the device back into operation. To circumvent the above limitations associated with the remote production of PET radiopharmaceuticals, the authors have investigated the use of laboratory robotics as a flexible alternative to the synthesis of several ...
We study the expected properties of starbursts in order to provide the point of reference for interpretation of high-z galaxy surveys and of very metal-poor galaxies. We concentrate mainly on the UV characteristics such as the ionizing spectra, the UV continuum, the Ly alpha and HeII 1640 A line and two-photon continuum emission. We use evolutionary synthesis models covering metallicities from Pop III to solar and a wide range of IMFs. We also combine the synthetic SEDs with the CLOUDY photoionization code for more accurate predictions of nebular emission, and to study possible departures from case B assumed in the synthesis models. The ionizing fluxes, UV continuum properties, and predicted Ly alpha and HeII 1640 A line strengths are presented for synthesis models covering a wider range of parameter space than our earlier calculations. Strong departures from case B predictions are obtained for Ly alpha and two-photon ...
Measurement of redshifted 21-cm emission from neutral hydrogen promises to be the most effective method for studying the reionisation history of hydrogen and, indirectly, the first galaxies. These studies will be limited not by raw sensitivity to the signal, but rather, by bright foreground radiation from Galactic and extragalactic radio sources and the Galactic continuum. In addition, leakage due to gain errors and non-ideal feeds conspire to further contaminate low-frequency radio obsevations. This leakage leads to a portion of the complex linear polarisation signal finding its way into Stokes I, and inhibits the detection of the non-polarised cosmological signal from the epoch of reionisation. In this work, we show that rotation measure synthesis can be used to recover the signature of cosmic hydrogen reionisation in the presence of contamination by polarised foregrounds. To achieve this, we apply the rotation measure synthesis technique to ...
The concept of nanocrystal conversion chemistry, which involves the use of pre-formed nanoparticles as templates for chemical transformation into derivative solids, has emerged as a powerful approach for designing the synthesis of complex nanocrystalline solids. The general strategy exploits established synthetic capabilities in simple nanocrystal systems and uses these nanocrystals as templates that help to define the composition, crystal structure, and morphology of product nanocrystals. This article highlights key examples of 'conversion chemistry' approaches to the synthesis of nanocrystalline solids using a variety of techniques, including galvanic replacement, diffusion, oxidation, and ion exchange. The discussion is organized according to classes of solids, highlighting the diverse target systems that are accessible using similar chemical concepts: metals, oxides, chalcogenides, phosphides, alloys, intermetallic compounds, sulfides, and ...
We presented a simple approach for in-situ synthesis of poly(dimethylsiloxane) (PDMS)-gold nanoparticles composite film based on the special characteristics of PDMS itself. It is an environmentally safe synthesis method without the requirement of additional reducing/stabilizing agents. The region where the resulting gold nanoparticles distribute (in the matrix or on the surface of the polymer) and the size of the nanoparticles, as well as the colour of the free-standing films, can be simply controlled by adjusting the ratio of curing agent and the PDMS monomer. The chemical and optical properties of these composite films were studied. Using such a method, gold nanoparticle micropatterns on PDMS surfaces can be performed. And based on the gold nanoparticles micropattern, further modification with antibodies, antigens, enzymes and other biomolecules can be achieved. To verify this ability, an immobilized glucose oxidase (GOx) reactor in ...
Glycosaminoglycan synthesis by two subpopulations of a mouse mammary tumor cell line was compared. The two sublines express distinctly different growth characteristics in vitro and in vivo which indicate differences in growth regulation. Newly made glycosaminoglycans were recovered from the culture media, the cell surfaces, and residual cellular material. The cell population which grows more aggressively in vivo (+SA subline, a subline that grows in soft agarose) incorporated about 8 times more (/sup 14/C)glucosamine per cell into total glycosaminoglycans than did the slower-growing population (-SA subline, which does not grow in soft agarose). Appropriate control experiments indicated that the apparent difference in rates of synthesis was not due to discrepancies in glucosamine uptake. The main residual cellular molecule labeled was heparan sulfate, but the predominant molecule at the cell surface and in the culture fluid was hyaluronic acid. ...
The Fluxnet synthesis dataset originally compiled for the La Thuile workshop contained approximately 600 site years. Since the workshop, several additional site years have been added and the dataset now contains over 920 site years from over 240 sites. A data refresh update is expected to increase those numbers in the next few months. The ancillary data describing the sites continues to evolve as well. There are on the order of 120 site contacts and 60proposals have been approved to use thedata. These proposals involve around 120 researchers. The size and complexity of the dataset and collaboration has led to a new approach to providing access to the data and collaboration support and the support team attended the workshop and worked closely with the attendees and the Fluxnet project office to define the requirements for the support infrastructure. As a result of this effort, a new website (http://www.fluxdata.org) has been created to provide access to the Fluxnet ...
Until now the assumption has been that synthesis gas - mixtures of carbon monoxide and hydrogen - would be the principal source for many of the chemicals and fuels to be made via C/sub 1/ chemistry. Efforts to make cheap synthesis gas continue. But the pressure to circumvent the stranglehold that OPEC has on petroleum has caused other avenues to be explored. The current oversupply of natural gas offers an interim solution to the problem of nonpetroleum alternate source materials for C/sub 1/ chemicals production. The paper discusses the constraints and advantages of four processes: conventional steam reforming, steam reforming with oxygen secondary, partial oxidation, and catalytic partial oxidation. The end product in all cases is methanol. Direct use of methanol as a fuel has encountered numerous difficulties. conversion of methanol is, thus, of more immediate interest in C/sub 1/ chemistry. The Mobil MTG process and its second-generation ...
The effect of hydrogen sulfide (H2S) on the chemical looping combustion of coal-derived synthesis gas with bentonite-supported metal oxidesssuch as iron oxide, nickel oxide, manganese oxide, and copper oxideswas investigated by thermogravimetric analysis, mass spectrometry, and X-ray photoelectron spectroscopy (XPS). During the reaction with synthesis gas containing H2S, metal-oxide oxygen carriers were first reduced by carbon monoxide and hydrogen, and then interacted with H2S to form metal sulfide, which resulted in a weight gain during the reduction/sulfidation step. The reduced/sulfurized compounds could be regenerated to form sulfur dioxide and oxides during the oxidation reaction with air. The reduction/oxidation capacities of iron oxide and nickel oxide were not affected by the presence of H2S, but both manganese oxide and copper oxide showed decreased reduction/oxidation capacities. However, the rates of reduction and oxidation ...
This paper presents a series of structural modifications of soybean oils for lubricant. The reaction was monitored and products were confirmed by NMR and FTIR. The structural modification is carried out in four stages, (1) synthesis of soybean oil isooctyl ester from soybean oil; (2) synthesis of epoxy-soybean oil isooctyl ester from soybean oil isooctyl ester; (3) synthesis of hydroxylated products from epoxy soybean oil isooctyl ester with fatty acid; (4) esterification of the hydroxylated product with anhydride. Rheological behaviour of the products was measured. Pour points of the products (3) were observed as low as -24 C (lauric acid) and -15 C (isooctanoic acid) respectively. When the hydroxyl groups in the products were esterified with and acid anhydride, the pour points were became higher, which were -21 C (lauric acid) and -6 C (isooctanoic acid) without pour point depressant, and -27 C (lauric acid) and -24 C ...
This report details the status of the Biological Conversion of Synthesis Gas Project. The following tasks are described as being completed: (1) the test plan, (2) culture development, and (3) the mass transfer/kinetic studies. The bioreactor studies (Task 4) are underway. The continuous stirred tank reactor system for the conversion of H{sub 2}S to elemental sulfur using Chlorobium thiosulfatophilum has been studied for varying light intensities. The system was also modified to include both sulfur recovery and cell recycle using ceramic membranes. Studies were also performed to observe the effects of cell recycle using a polysulfone hollow filter membrane module. Work on Task 5, limiting conditions/scale-up, includes a scale-up study with three different size reactors to establish the optimum operating conditions for hydrogen production from synthesis gas by the biological water-gas shift reaction using the photosynthetic bacterium ...
A new automated synthesis procedure of 1-H-1-(3-[18F]fluoro-2-hydroxypropyl)-2-nitroimidazole ([18F]FMISO), a specific hypoxia imaging agent with great significances for the noninvasive, dynamic hypoxia evaluation of cancer, was developed by modifying Explora FDG4 module, a commercial [18F]FDG production system, in this study. Its radiochemical synthesis was carried out via two sequent reaction steps, i.e. the nucleophilic displacement of labeling precursor 1-(2?-nitro-1?-imidazolyl)-2-O-tetrahydropyranyl-3-O-tosyl-propaned iol (NITTP) with activated 18F- ion at 100 ?C for 8 minutes, and the following hydrolysis with 1M HCl at 100 ?C for 5 minutes and neutralization with 1M NaOH. Two-pot reaction with two independent separations was adopted to assure the good separation of final product vi...
W have introduced template-synthesized metal phosphate nanoparticle labels for electrochemical immunoassay. Such use of an apoferritin template offers a simple and convenient route to prepare metallic nanoparticle labels for electrochemical immunoassays and avoid the complicated and time-consuming nanoparticle synthesis process (QD synthesis). Releasing metal ions from metal phosphate in an acetate buffer (pH 4.6) eliminates the harsh condition in the traditional metallic nanoparticle dissolution (e.g., strong acid dissolution of QDs and gold nanoparticles). This method is ultrasensitive and its DL is low to 77fM. The simultaneous detection of multiple protein targets is easily performed by using different metal phosphate nanoparticle labels (cadmium phosphate and lead phosphate). This approach can be extended to prepare multiple metal (such as zinc, lead, cadmium, copper, indium, gold, silver) phosphate nanoparticle labels or hybrid metal ...
Similar to stand-alone ER-MCFC power systems industrial ammonia production facilities include hydrogen-rich synthesis-gas production. Therefore, integration of ER-MCFC stacks in a conventional industrial ammonia plant was investigated. By preliminary process design calculations three promising process structures were evaluated: (1) ER-MCFC is fed by the ammonia plant`s steam-reformer; anode off-gas to firing (2) similar to structure 1; in this case the anode off-gas is redirected to the ammonia process (3) ER-MCFC is fed by ammonia-synthesis purge gas The results indicate that for options 1 and 3 a return-on-investment for the ER-MCFC of around 8% is achievable at a stack cost of $250/kW and a revenue of 7c/kWh. Option 2 is not profitable, because of the associated reduction in ammonia production. The degree of hydrogen-utilization in the ER-MCFC to be selected for maximum profit varies with the process structure and indicates that there is ...
Low pressure silane plasmas are known for their ability to synthesize silicon nanoparticles via gas phase nucleation. While in the past this particle formation has often been considered from the viewpoint of a contamination problem in semiconductor processing, we here describe a silane low pressure plasma that enables the synthesis of highly oriented, cubic-shaped silicon nanocrystals with a rather monodisperse size distribution. These silicon nanocubes have successfully been used in the manufacture of single nanoparticle vertical transistors. We discuss the advantages of this new paradigm of building nanoelectronic devices. The plasma synthesis process is characterized in more detail than in prior work. The particle nucleation, growth and shape evolution are studied. Results indicate that the process provides two spatially distinct zones: a diffuse plasma for particle growth and a constricted plasma zone for particle annealing. Measurements of ...
We propose and demonstrate a facile room-temperature synthetic method for obtaining water-soluble magnetic Fe3O4 nanoparticles (NPs) by combining the in situ synthesis and decomposition of a magnetic polymer hydrogel. The Fe3O4 NPs with average diameters of 6.3-8.3nm were synthesized in a cross-linked polyacrylamide (PAAm) hydrogel by coprecipitating iron ions. The decomposition of the magnetic polymer hydrogel by an aqueous solution of sodium hydroxide led to the transfer of Fe3O4 NPs into the aqueous medium. The NPs can be dispersed stably in water for more than three months. The Fe3O4 NPs were characterized by X-ray photoelectron spectra (XPS), X-ray powder diffraction (XRD), transmission electron microscope (TEM), and Fourier transform infrared spectroscopy (FT-IR). The saturation magn...
Concerning high performance composite solid propellant BAMO and BAMO-based copolymers, synthetic method and properties of them were studied. Comparison graph of theoretical specific impulse for various propellants were shown, by that, reason why highest specific impulse BAMO was selected as direction of the study. As the orientation of synthesis, those were indicated that radicals at both ends should be hydroxyl so as urethane bonding was available, that liquid at normal temperature was required for easy handling, and that glass transition temperature is required to be low enough. Synthesis was conducted by ring-opening polymerization of ring ether detail procedures of which were explained. Measurements of properties was performed for thermochemical properties, thermal decomposition, combution heat, and friction sensitivity test to confirm safety. As the result, those were understood that thermal decomposition was divided into two phases, rapid ...
Many advances have been carried out on the estrogens, GnRH and endocannabinoid system that have impact in the reproductive field. Indeed, estrogens, the generally accepted female hormones, have performed an unsuspected role in male sexual functions thanks to studies on non-mammalian vertebrates. Similarly, these animal models have provided important contributions to the identification of several GnRH ligand and receptor variants and their possible involvement in sexual behavior and gonadal function regulation. Moreover, the use of non-mammalian animal models has contributed to a better comprehension about the endocannabinoid system action in several mammalian reproductive events. We wish to highlight here how non-mammalian vertebrate animal model research contributes to advancements with i...
a-Dystroglycan is an extracellular adhesion protein that is known to interact with different ligands. The interaction is thought to stabilize the integrity of the plasma membrane. The N-terminal part of a-dystroglycan may be proteolytically processed to generate a small 38kDa protein (a-DG-N). The physiological significance of a-DG-N is unclear but has been suggested to be involved in nerve regeneration and myelination and to function as a potential biomarker for neurodegenerative and neuromuscular diseases. In this report we show that a-DG-N is released into different body fluids, such as lachrimal fluid, cerebrospinal fluid (CSF), urine and plasma. To investigate the significance of a-DG-N in CSF we examined the levels of a-DG-N and known neurodegenerative markers in CSF from patients di...
A promising drug target currently under investigation to improve cognitive deficits in neuropsychiatric and neurological disorders is the neuronal nicotinic alpha7 acetylcholine receptor (a7nAChR). Improving cognitive impairments in diseases such as Alzheimer's (AD) and schizophrenia remains a large unmet medical need, and the a7nAChR has many properties that make it an attractive therapeutic target. The a7nAChR is a ligand gated ion channel that has particularly high permeability to Ca^2^+ and is expressed in key brain regions involved in cognitive processes (e.g., hippocampus). The a7nAChRs are localized both pre-synaptically, where they can regulate neurotransmitter release, and post-synaptically where they can activate intracellular signaling cascades and influence downstream processes...
Coordination of CoCl2 solutions to the silica polyamine composite, WP-1, made with the branched polymer polyethylenimine (PEI) shows irreversible binding resulting from surface oxidation of the Co2+-Co3+. This is not the case for the silica polyamine composite BP-1 made with the linear polymer polyallylamine where reversible binding and no oxidation is observed. These observations suggested that oxidation of the cobalt was related to the greater coordination number available with the branched polyamine relative to the linear polyamine. A study of the kinetics of cobalt binding to WP-1 indicated initial loading of Co2+ at relatively low coordination number followed by desorption of Co2+ leading to oxidation and irreversible binding. Exclusion of oxygen from the composite-cobalt solution mix...
Fgf receptor 2c (Fgfr2c) was expressed in mature adipocytes of mouse white adipose tissue (WAT). To examine the role of Fgfr2c in mature adipocytes, we generated adipocyte-specific Fgfr2 knockout (Fgfr2 CKO) mice. The hypertrophy impairment of adipocytes in the mesenteric WAT but not in the subcutaneous WAT and decreased plasma free fatty acid (FFA) levels were observed in Fgfr2 CKO mice. Although the expression of genes involved in adipocyte differentiation and lipid metabolism in the mesenteric WAT was essentially unchanged, the expression of uncoupling protein 2 potentially involved in energy dissipation was significantly increased. Among potential Fgf ligands for Fgfr2c, Fgf9 was preferentially expressed in the mesenteric WAT. The present findings indicate that Fgfr2c potentially activ...
An hydrazone derivative, 1,2-cyclohexanedione bis-benzoyl-hydrazone (1,2-CHBBH), has been used as a selective reagent for an advanced environmental application consisting of separating the different species of nickel in natural waters by solvent extraction. The effects of pH and reagent concentration on the extraction process were studied, as well as the influence of both organic (humic acids) and inorganic ligands (Cl-). Under natural conditions, organic and inorganic nickel species presented different extraction behaviors, and the variations in extraction yields could be correlated with the concentrations of organic complexes in the samples, allowing the separation of labile and non-labile nickel species in both fresh and marine waters.
Studies addressed to a deep understanding of the structure/property relationship on the near infrared (NIR)-emissive erbium-quinolinolate complexes, which are of interest for low-cost photonic systems, are reviewed. The role of the 8-quinolinolate ligand (Q), which studies also as sensitizer to overcome the weak absorptivity of lanthanide ion, is discussed. Synthetic and structural aspects are reported to revise the old assumption that these complexes are analogous in structure to AlQ3 and to point out the specificity of the lanthanide coordination chemistry. In fact depending on reaction conditions, species with high coordination numbers and differing for nuclearity and stoichiometry have been isolated and fully characterized. In some instances it has been shown that coordinated water mol...
Colloidal nanocrystals attract significant interest due to their potential applications in electronic, magnetic, and optical devices. Nanocrystal supercrystals (NCSCs) are particularly appealing for their well ordered structure and homogeneity. The interactions between organic ligands that passivate the inorganic nanocrystal cores critically influence their self-organization into supercrystals, By investigating the mechanical properties of supercrystals, we can directly characterize the particle-particle interactions in a well-defined geometry, and gain insight into both the self-assembly process and the potential applications of nanocrystal supercrystals. Here we report nanoindentation studies of well ordered lead-sulfide (Pbs) nanocrystal supercrystals. Their modulus and hardness were found to be similar to soft polymers at 1.7 GPa and 70 MPa respectively and the fractures toughness was 39 KPa/m1/2, revealing the extremely brittle nature of these materials.
Single-crystalline CeRh{sub 2}Si{sub 2} and CePd{sub 2}Si{sub 2} were grown by the Czochralsky pulling method and the temperature dependence of magnetic susceptibility was investigated. The crystalline electric field (CEF) states in each compound were determined by considering the tetragonal CEF Hamiltonian with mean-field approximation. Interactions between Ce{sup 3+} ion and the surrounding ligands in CeRh{sub 2}Si{sub 2} turned out to be strong and highly anisotropic in comparison to CePd{sub 2}Si{sub 2}. (orig.) 10 refs.
One of the research challenges in oncology is to develop new biochemical methods for noninvasive tumor therapy evaluation to determine whether the chemotherapeutics is effective. Vascular endothelial growth factor (VEGF) was labeled with radioiodine and evaluated in vitro as well as in vivo, using A2058, a melanoma cell line overexpressing VEGFR-1 and -2. Saturation binding analysis with [{sup 125}I]-VEGF resulted in a K {sub d} of 0.1 nM. Internalization assays indicate the preserved ligand induced internalization and metabolization of the tracer. Biodistribution studies with [{sup 123}I]-VEGF in wild type and A2058 tumor-bearing athymic mice showed low background activity and a tumor to reference tissue ratio of maximum 6.12. These results suggest that [{sup 123}I]-VEGF is a potentially suitable tracer for tumor therapy evaluation.
The authors have cloned and determined the entire nucleotide sequence of cDNAs corresponding to the putative {alpha} subunits of the human and rat mast cell high-affinity IgE receptors. Both human and rat cDNAs encode an NH{sub 2}-terminal signal peptide, two immunoglobulin-like extracellular domains (encoded by discrete exons), a hydrophobic transmembrane region, and a positively charged cytoplasmic tail. The human and rat {alpha} subunits share an overall homology with one another and the immunoglobulin gene family, suggesting that they arose from a common ancestral gene and continue to share structural homology with their ligands. In addition, the rat gene is transcribed into at least three distinct forms, each of which yields a somewhat different coding sequence.
The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.
Single crystals of ytterbium tartrate trihydrate have been grown by gel method using silica and agar-agar gels as media of growth. The medium of growth influences the morphology of grown crystals, silica gel yielding single and polycrystalline in the form of spherulites whereas agar-agar gel leading to growth of single and twinned crystals. Materials grown as single crystals have been characterized by using optical and scanning electron microscopy (SEM), EDAX, XRD, FT-IR, CHN and thermogravimetric techniques. The stoichiometry of the grown single crystals is suggested to be Yb(C4H4O6) (C4H5O6).3H2O. The FT-IR spectrum shows the presence of singly as well as doubly ionized tartrate ligands. Results of thermal analysis indicate that the material is thermally stable up to a temperature of 200...
New Schiff base chelating ligands were synthesized by reacting equimolar quantities of 2,3-dimethyl-4-formyl-1-phenyl-3-pyrazoline-5-one and o-anisidine, p-anisidine, m-anisidine, o-toluidine, p-toluidine, m-toluidine, 2,6-xylidine or 2,4-xylidine in ethanol medium. Their subsequent reaction with gadolinium (III) nitrate hexahydrate in 2:1 molar ratio gave complexes that were characterized by elemental analyses, molar conductances, magnetic measurements, electronic and I.R. spectral studies. All the chelates were found to be non-electrolytic in nature. (author). 15 refs., 1 fig., 1 tab.
The aim of this work was to study the energy transfer mechanisms from the ligand to the central lanthanide ion of tetracycline-europium (Tc-Eu) complex. The absorption spectra of a EuCl{sub 3}.H{sub 2}O solution was measured and absorption cross-section of Eu{sup 3+} was estimated. The observed overlap predicts a resonant energy transfer from Tetracycline to Eu{sup 3+}. The microscopic parameter of energy transfer was obtained using the overlap integral calculation considering a dipole-dipole energy transfer mechanism and results were compared considering an energy transfer by exchange. In this work, we report also the optical properties of Tc-Eu complex when urea hydrogen peroxide is added to the aqueous solution.
The absorption and magnetic circular dichroism spectra of [N(n-Bu)_4]"+[(MeCp)_3PrCl]"- dissolved in 2-MeTHF were measured at room and at low temperatures. On the basis of these spectra the crystal field splitting pattern could be derived. The parameters of an empirical Hamiltonian were fitted to the energies of 42 levels to give an r.m.s. deviation of 23 cm"-"1. From the crystal field parameters obtained the crystal field strength of the ligand collective was estimated. Compared with neutral Cp_3Pr circle B complexes the crystal field strength of the anionic [(MeCp)_3PrCl]"- moiety is unusually low. (orig.)
The distribution of the central benzodiazepine receptor specific ligand iodine-123 iomazenil was investigated in seven human adults from whole-body scans, blood samples and urine collected up to 24 h after injection. Using 12 source organs, the MIRD method was applied to calculate the absorbed radiation dose of the radioligand in various organs. The urinary bladder wall (0.15 mGy/MBq), lower large intestinal wall (0.071 mGy/MBq) testes (0.044 mGy/MBq) and upper large intestined wall (0.038 mGy/MBq) received the highest absorbed doses. The average effective dose equivalent of "1"2"3I-IBZM for adults was estimated to be 0.033 mSv/MBq. (orig.).
The present work focuses on investigations of a highly selective ligand for Am(III)/Ln(III) separation: bis-triazinyl-pyridine (BTP). By means of nano-electro-spray mass spectrometry, complex formation of BTP with selected elements of the lanthanide series is investigated. We show that the diluent drastically influences complex speciation. Measurements obtained in the extraction-relevant diluent 1-octanol show the occurrence of Ln(BTP){sub i} (i 1-3) species in different relative abundances, depending on the lanthanide used. Here, the relative abundances of the Ln(BTP){sub 3} complexes correlate with the distribution ratios for extraction to the organic phase of the respective lanthanide. (authors)
Sols of silver nanoparticles in toluene were studied by broadband dielectric spectroscopy (10?3?105 Hz). The frequency dependences of the specific alternating current (ac) conductivity and the complex electric modulus were used to estimate the temperature/frequency intervals of long- and short-range charge transfer occurs, respectively. A considerable increase (by more than 30 ?C) in the Vogel temperature T 0 and the glass transition temperature T g in sols compared with the pure solvent was found. It can be hypothesized that these cooperative effects reflect the initial stage of the superlattice formation. Although the dielectric characteristics of sols are generally controlled by the conductivity relaxation, the dielectric response was observed in the high-frequency range (1?103 Hz) at l...
Platinum and ruthenium in carbon supported Pt and Pt-Ru catalysts were determined by direct and derivative spectrophotometric methods. Complexes of platinum and ruthenium with SnCl(3)(-) ligands (tin(II) chloride in HCl) were used to determine both metals in solutions obtained after digestion of the samples of the catalysts. Platinum in the Pt/C catalyst can be determined in solutions obtained by digestion of the samples in aqua regia. Derivative spectrophotometry was used to determine both metals in the presence of each other in solutions obtained after digestion of samples of the Pt-Ru/C catalyst in the mixture of HCl+HNO(3) (6:1). The first derivative at 377 nm (;zero-crossing' point of ruthenium) and the second-derivative values at 495 nm (;zero-crossing' point of platinum) were used to estimate the concentration of platinum and ruthenium, respectively. PMID:18967441
Carbohydrate and nucleotide structural determination using modern spectroscopic techniques is dependent on our ability to label oligonucleotides and oligosaccharides with stable isotopes. Uniform Carbon 13 and Nitrogen 15 labeling of oligonucleotides is important to present-day efforts, which are focused on determining the structure of relatively small oligosaccharides and oligonucleotides, which form the elements of larger structures. Because of the relatively recent interest in three-dimensional structure, the development of techniques used to label them has lagged behind parallel techniques used to label peptides and proteins. Therefore, this group`s discussion focused primarily on problems faced today in obtaining oligonucleotides labeled uniformly with carbon 13 and nitrogen 15.
Analyses of food-borne pathogens are of great importance in order to minimize the health risk for customers. Thus, very sensitive and rapid detection methods are required. Current conventional culture techniques are very time consuming. Modern immunoassays and biochemical analysis also require pre-enrichment steps resulting in a turnaround time of at least 24 h. Biomagnetic separation (BMS) is a promising more rapid method. In this study we describe the isolation of high affine and specific peptides from a phage-peptide library, which combined with BMS allows the detection of Salmonella spp. with a similar sensitivity as that of immunomagnetic separation using antibodies.
Apelin is a peptide known as the ligand of the G-protein-coupled receptor APJ. Several active apelin forms exist such as apelin-36, apelin-17, apelin-13, and the pyroglutamated form of apelin-13. Apelin and APJ are expressed in the central nervous system, particularly in the hypothalamus and in many peripheral tissues. Apelin has been shown to be involved in the regulation of cardiovascular and fluid homeostasis, food intake, cell proliferation, and angiogenesis. In addition to be an ubiquitous peptide, apelin is also produced and secreted by adipocytes and thus considered as an adipokine. This has opened a new field of investigation establishing a link between apelin and metabolic disorders (obesity, type 2 diabetes, etc.) which is the focus of the present review. Several studies, but not...
The monoanionic bidentate Schiff base, N-(phenolyl)-benzaldimine (HL), has been employed to synthesize a new vanadium(IV) complex of general composition [VO(L)2] (where L = O, N donor of Schiff base). The ligand and complex have been fully characterized by elemental analyses, molar conductance data, FT-IR, 1H- and 13C-NMR, and UV-Vis spectroscopies. Oxidation of alcohols to their corresponding aldehydes and ketones was conducted by this complex catalyst using Oxone as oxidant under biphasic reaction conditions (CH2Cl2/H2O) and tetra-n-butylammonium bromide as phase transfer agent under air at room temperature.
A new procedure for preparing an 211At-labeled radiopharmaceutical is suggested. The 211At? anion forms a strong bond with the Rh3+ cation incorporated in the complex with a thiother ligand, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (16-S4-diol). The reaction conditions are optimized with 131I as astatine analog. The complexes are studied by paper electrophoresis, ion exchange, and thin-layer chromatography. The kinetics of the addition of the 131I? anion to Rh(16-S4-diol) and the dependence of the yield of the forming complex 131I-Rh(16-S4-diol) on the temperature, solution acidity, and reactant concentrations are examined. Taking into account the results obtained, the complex 211At-Rh(16-S4-diol) is prepared by adding astatide (211 At?) to equivalent amounts of RhCl3 and the tetrathioe...
Secondary energy can be described as a surplus of electrical energy in a hydropower because the lower demand of energy in some period of the day and the excess of water in the reservoir during the rainy periods. This study proposes the using of the excess of energy at Itaipu Bi nacional for electrolytically hydrogen production and ammonia for nitrogenous fertilizers. Ammonia is a raw material for nitrogenous fertilizers synthesis and produced using hydrogen and nitrogen from the atmosphere. This paper determines the minimal cost of hydrogen production and the capacity of hydrogen production, with this data and according the ammonia market for nitrogenous fertilizers in the Centre/South region was estimated the better capacity of ammonia production for one plant near Itaipu. The process of ammonia production using energy excess is the most environmental acceptable. (author)
The indirect conversion of coal to liquid hydrocarbons via steam gasification followed by synthesis gas (CO/H/sub 2/) chemistry has been the subject of intensive study for a number of decades. A key technological challenge facing researchers in this area is control over the product distribution during the hydrocarbon synthesis step. In the case of iron Fischer-Tropsch catalysts, it has been known that the addition of alkali to the metal catalyst has a significant impact on the product distribution. Iron catalysts treated with alkali produce less methane more alkenes and higher molecular weight products. In spite of numerous investigations, the details of this promotional effect are not understood on a molecular level. To explore the role of alkali in the surface chemistry of iron catalysts, the authors have carried out a combined surface science and catalytic kinetic study of a model iron catalyst with and without surface alkali.
We perform an analysis of the production of elements with mass number A {ge} 12 in a standard Big Bang Nucleosynthesis scenario. The goal is to provide a more accurate estimate of the very low and yet poorly explored abundance of such elements, relevant for the pristine Population III stars. We examine the synthesis channels for these elements in a critically revised and updated version of the Wagoner-Kawano code, as well as in a further enlarged version including four additional nuclides and a significantly extended nuclear network. Our results show no major discrepancies with the ones obtained using a smaller nuclear network. The robustness of the standard predictions--the early generation of star developed in a metal-free environment--is confirmed.
Methods for the synthesis and quantitation of the novel choline analogues, telluronium choline and acetyltelluronium choline, are described. An assay procedure utilizing pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) with cold trapping was developed with [2H4]telluronium choline and [2H4]acetyltelluronium choline as internal standards. The telluronium compounds were ion-pair extracted from tissue with dipicrylamine, washed with 2-butanone, and pyrolyzed prior to GC-MS analysis. The compounds were monitored using selected ion monitoring at m/z 232 and m/z 190 for acetyltelluronium and telluronium choline, respectively, and at m/z 236 and m/z 194 for the analogous deuterated internal standards. The assay was linear over a range of 20 pmol-20 nmol of compound taken through the assay. PMID:8130881
Starting from commercial 4-chloro-3-nitroaniline, through a 5 step synthesis, 3-azido-4-chlorophenylisothiocyanate was prepared and reacted with ["3H]-methylamine. The latter was obtained by three methods: (i) ["3H]-LiA1T_4 reduction of benzylcarbamate gave rise to ["3H]-methylamine (S.A.: > 70 Ci/mmol). (ii) Catalytic reduction of HCN with "3H_2 lead to ["3H]-CH_3NH_2 (S.A.: 0.7 Ci/mmol). (III) Schmidt rearrangement of ["3H]-sodium acetate gave ["3H]-CH_3NH_2 (S.A.: 29 Ci/mmol). (author).
Two no-carrier-added "1"2"5I-labelled photoaffinity rapamycin analogs were prepared: 7-demethoxy-7-(4-azido-3-"1"2"5I-benzyloxy) rapamycin and its C_2_8-C_2_9 seco analog. The key reactions of the synthesis were substitution of the C_7 methoxyl of rapamycin with 4-azido-3-tributylstannylbenzyloxy group, exchange of tributyltin with "1"2"5I using Na"1"2"5I and Chloramine-T, and a ZnCl_2 mediated retro-Aldol cleavage of the C_2_8-C_2_9 bond of rapamycin. (author).
We have developed a method for the synthesis of C-11 iodoantipyrine. Carbon-11-labeled methyl iodide, prepared from /sup 11/CO2, was used to methylate 3-methyl-1-phenyl-2-pyrazolin-5-one to form C-11 antipyrine. Following silica-gel column chromatography and iodination, radiochemical purity of the C-11 iodoantipyrine was more than 99.5%, with a 10% yield and a specific activity of 30 mCi/mumol. Preliminary animal studies showed complete cerebral extraction and local cerebral blood-flow values that were within 4.6% of those obtained using C-14 iodoantipyrine. The C-11 analog, with positron emission tomography, will facilitate local cerebral blood-flow studies in human subjects.
The synthesis of 3-O-sulphamoyl derivatives of 1,2:5,6-di-O-isopropylidene-#alpha#-D-glucofuranose, 1,2-O-isopropylidene-#alpha#-D-glucofuranose, and 5,6-di-O-acetyl-1,2-O-isopropylidene-#alpha#-D-glucofuranose is described. A study of the reactions of carbohydrate chlorosulphates with azide has demonstrated the relative case with which certain chlorosulphonyloxy groups may be converted into azidosulphates. These azidosulphates could have potential synthetic value if a facile method for their conversion into sulphamoyl (aminosulphate) derivatives were available, since some sulphamoyl carbohydrates have been shown to possess antibiotic and antitrypanosomal activity. This report deals with the application of sodium borohydride and platinum oxide-hydrogen to the reduction of some 3-O-azidosulphate glucofuranose derivatives. "1H-n.m.r. spectra and infrared spectra were used.
In this work it is made a study of the structure and electric properties of chlorate polyethylene (PE-CI) with double and simple bonds obtained by continuous plasma with resistive coupling to 13.5 MHz. The synthesis conditions are power between 10 and 14 W and pressure of (6-7) x 10{sup -2} Torr. The synthesized PE-Cl in that way is soluble in acetone what indicates that probably is formed of short chains and not it shows the generalized inter crossing that is presented in some syntheses by plasma and that it can degrade the electric properties of these polymers. The IR and XPS analysis show the vibration of the C-C, C=C and C-CI bonds. The morphology of the polymer after being dissolved shows a compact and flat configuration. The electric conductivity has an approximately lineal behavior in an interval of 35 to 90% of relative humidity. (Author)
The synthesis and structures of three new compounds are reported. [Mg2{PhP(Se,O)Se-Se(O,Se)PPh}2(thf)7(H2O)3] (1), [Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (2), and [Mn{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (3) were prepared by treatment of Woollins reagent [PhP(Se)(m-Se)]2 with the corresponding hydrated metal acetates.
Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface ...
We have studied the ion-beam synthesis of GaSb nanocrystals in Si by high-fluence '' hot '' implantation of Sb and Ga ions followed by thermal annealing. The Rutherford backscattering, transmission electron microscopy/transmission electron diffraction, Raman spectroscopy and photoluminescence were used to characterize the implanted layers. It was found that the nanocrystal size increases from 5 to 60 nm in the samples annealed at 900"oC up to 20-90 nm in those annealed at 1100"oC. For the samples annealed at 900"oC a broad band in the region of 0.75-1.05 eV is registered in the photoluminescence spectra. The nature of this photoluminescence band is discussed. (author)
Development of useful high-critical-temperature (high-{Tc}) superconductors requires synthesis of superconducting compounds; fabrication of wires, tapes, and films from these compounds; production of composite structures that incorporate stabilizers or insulators; and design and testing of efficient components. This report describes technical progress of research and development efforts aimed at producing superconducting components based on the Y-Ba-Cu, Bi-Sr-Ca-Cu, Bi-Pb-Sr-Ca-Cu, and Tl-Ba-Ca-Cu oxides systems. Topics discussed are synthesis and heat treatment of high-{Tc} superconductors, formation of monolithic and composite wires and tapes, superconductor/metal connectors, characterization of structures and superconducting and mechanical properties, and fabrication and properties of thin films. Collaborations with industry and academia are also documented. 10 figs.
One-step synthesis of Pt-loaded carbon nanoparticles including single-wall carbon nanohorns (SWNHs) by arc plasma in liquid nitrogen was demonstrated using Pt-contained graphite anode. The size distribution of Pt particles can be controlled by adjusting the concentration of Pt in the graphite anode. In the observation by transmission electron microscope, the diameter of less than 5 nm of Pt particles were observed as approximately 90% among the Pt particles when Pt was contained in the anode at 1.3 at.%. When Pt concentration in the anode was decreased to 0.4 at.%, the percentage of Pt particles whose diameter is less than 5 nm decreased to approximately 60%. It was verified that the as-grown Pt-loaded products produced by this method can be useful for the power generation by polymer electrolyte fuel cell.
The cover picture shows the fertile combination of synthetic chemistry and experimental physics, both permanently making central contributions to hot scientific topics in spite of being classical scientific disciplines with long-standing traditions. The displayed scientist struggles with the synthesis of cruciform structures (displayed on the black board) for single-molecule-transport investigations in a mechanically controlled break junction setup (sketched in the inset at the upper right corner). More information on the design and synthesis of the cruciform structures, such as their immobilization experiments, is found in the article by M. Calame, M. Mayor et al. on p. 833 ff. Serafin Pazdera is greatly acknowledged for the cover artwork.
The binding energy parameter #lambda# plays an important role in common envelope evolution. Previous works have already pointed out that #lambda# varies throughout the stellar evolution, though it has been adopted as a constant in most of the population synthesis calculations. We have systematically calculated the binding energy parameter #lambda# for both Population I and Population II stars of masses 1-20 M _s_u_n, taking into account the contribution from the internal energy of stellar matter. We present fitting formulae for #lambda# that can be incorporated into future population synthesis investigations. We also briefly discuss the possible applications of the results in binary evolutions.
Racemic and enantiomerically pure b-amino-a-trifluoromethyl alcohols were obtained via sequential nucleophilic trifluoromethylation of selected a-imino ketones, derived from arylglyoxals, and subsequent removal of the MeO or Ph(Me)CH substituent, respectively, located at the N-atom. The obtained products, containing a primary amino group, were used for the synthesis of imidazole N-oxides bearing a trifluoromethyl group as a part of the N(1)-alkyl chain. Imidazole N-oxides with an electron-withdrawing ester group at C(4) underwent spontaneous isomerization under the reaction conditions, and the corresponding imidazol-2-ones derivatives were isolated as final products.
Abstract Under eons of evolutionary and environmental pressure, biological systems have developed strong and lightweight peptide-based polymeric materials by using the 20 naturally occurring amino acids as principal monomeric units. These materials outperform their man-made counterparts in the following ways: 1)-multifunctionality/tunability, 2)-adaptability/stimuli-responsiveness, 3)-synthesis and processing under ambient and aqueous conditions, and 4)-recyclability and biodegradability. The universal design strategy that affords these advanced properties involves -bottom-up- synthesis and modular, hierarchical organization both within and across multiple length-scales. The field of -biomimicry--elucidating and co-opting nature-s basic material design principles and molecular building blo...
Acute {gamma}-irradiation of rats at doses of 100 and 270 Gy stimulates lipid synthesis and changes the lipid composition of liver cell organelles. The content of cholesterol and cholesterol esters in microsomes increased at 100 Gy and decreased at 270 Gy, with total phospholipid content remaining unchanged. The lipid content in mitochondria decreased considerably 1 h after irradiation at 270 Gy. This change was significantly less pronounced 47 h later. Under chronic {gamma}-irradiation (0.129 Gy/day), cholesterol and cardiolipin in mitochondria increased. The changes in lipid content caused by acute irradiation are presumed to be related to activated synthesis of lipids in the liver. The modification of the lipid content of mitochondria observed in chronically irradiated rats may indicate that energy-metabolizing liver cell systems are involved in the adaptation to irradiation.
In situ synthesis of silver chloride (AgCl) nanoparticles was carried out under ambient conditions in nanoporous bacterial cellulose (BC) membranes as nanoreactors. The growth of the nanoparticles was readily obtained by alternating dipping of BC membranes in the solution of silver nitrate or sodium chloride followed by a rinse step. X-ray diffraction (XRD) patterns indicated the existence of AgCl nanoparticles in the BC and scanning electron microscopy (SEM) images showed that the AgCl nanoparticles well dispersed on the surface of BC and penetrated into the BC network. The AgCl nanoparticle-impregnated BC membranes exhibited high hydrophilic ability and strong antimicrobial activity against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). The preparative proced...
The status of commercial technology for indirect liquefaction, as exemplified by SASOL facilities in South Africa, is reviewed. The impact of substituting more advanced gasifiers and synthesis systems is then investigated. Slagging BGC/Lurgi, Texaco and Shell-Koppers gasifiers were substituted for the Dry Ash Lurgi units used at SASOL. SASOL SYNTHOL synthesis units were replaced by slurry phase Fischer-Tropsch units employing technology pioneered by Kolbel. The advanced systems were found to have a highly favorable impact on plant efficiency, product distribution and gasoline cost. If all the projected technical improvements can be realized for indirect liquefaction, the yields of refined transportation fuels per ton of coal will approach those anticipated for direct liquefaction processes.
A series of [60]fullerene-substituted phenylalanine (Baa) and lysine derivatives have been prepared by the condensation of 1,2-(4prime-oxocyclohexano)fullerene with the appropriately protected (4-amino)phenylalanine and lysine, respectively. Conversion of the imine to the corresponding amine is achieved by di-acid catalyzed hydroboration. The reduction of the imine is not accompanied by hydroboration of the fullerene cage. The [70]fullerene phenylalanine derivative has also been prepared as have the di-amino acid derivatives. The compounds were characterized by MALDI-TOF mass spectrometry, UV/Vis spectroscopy, and cyclic voltammetry. 1H and 13C NMR spectroscopy allowed the observation of diastereomers. Fullerene-substituted peptides may be synthesized on relatively large scale by solid-pha...
The paper proposes a concept of power driver for industrial thermonuclear reactor based on inertial thermonuclear synthesis (ITS). The circuit is based on the application of free electron laser (FEL) as a energy source for thermonuclear target compression which becomes feasible due to the application of a radically new circuit of FEL-amplifier. In the project under consideration the FEL-based laser system operates on the wave length of 0.5 micrometer. The full energy of laser radiation equals 1 MJ. This energy is delivered to the target in the pulse whose length is controlled within the range of 0.1-2 ns. The laser system brightness is 4 x 10"2"2 W cm"-"2. The FEL operating pulse repetition frequency is 40 Hz, full efficiency of electricity conversion into the energy of optical radiation is 11%. 9 refs., 3 figs., 2 tabs.
We report a solution-phase synthetic route to copper nanoparticles with controllable size and shape. The synthesis of the nanoparticles is achieved by the reduction of copper(II) salt in aqueous solution with hydrazine under air atmosphere in the presence of poly(acrylic acid) (PAA) as capping agent. The results suggest that the pH plays a key role for the formation of pure copper nanoparticles, whereas the concentration of PAA is important for controlling the size and geometric shape of the nanoparticles. The average size of the copper nanoparticles can be varied from 30 to 80 nm, depending on the concentration of PAA. With a moderate amount of PAA, faceted crystalline copper nanoparticles are obtained. The as-synthesized copper nanoparticles appear red in color and are stable for weeks, ...
Abstract Rationale, aims and objectives- Finding ways to incorporate disparate types of evidence into research syntheses has the potential to build a better evidence base for clinical practice and policy. Yet conducting such mixed research synthesis studies is challenging. Researchers have to determine whether and how to use adjusted and unadjusted quantitative findings in combination with each other and with qualitative findings. Methods- Among quantitative findings, adjustment for confounding, either via study design or statistical analysis, can be a considerable source of heterogeneity. Yet there is no consensus about the best way to synthesize findings resulting from different methods for addressing confounding. When synthesizing qualitative and quantitative findings, additional consid...
Biomass gasification provides the potential to efficiently and economically produce a renewable source of a clean gaseous fuel suitable for power generation or synthesis gas (syngas) applications. An important side benefit of the use of biomass is the effective minimization of the primary greenhouse gas, carbon dioxide (CO{sub 2}), by providing a means to close-loop the CO{sub 2} cycle. However, high molecular weight hydrocarbon constituents (tar) in the product gas from gasification can complicate the downstream uses of the gas. This paper discusses both the development of a low cost, disposable catalyst system that can eliminate these heavy hydrocarbons from the gas and the use of the catalyst in conjunction with the Battelle high-throughput gasification process for power generation and synthesis applications. (author)
Bio-inspired palladium nanoparticles were synthesized by using banana peel extract (BPE), a non-toxic eco-friendly material. Boiled, crushed, acetone precipitated, air-dried peel powder was used to reduce palladium chloride. The palladium nanoparticles were characterized by using UV-Visible spectroscopy, scanning electron microscope-energy dispersive spectra (SEM-EDS) and X-ray diffraction (XRD) analysis. Dynamic light scattering (DLS) studies revealed the average size of nanoparticles to be 50nm. Fourier transform infra red spectroscopy (FTIR) implicated the role of carboxyl, amine and hydroxyl groups in the synthetic process. This paper thus describes a novel green method for the synthesis of palladium nanoparticles.
A fundamental Doppler-like but asymmetric wave effect that shifts received signals in frequency in proportion to their respective source distances, was recently described as means for a whole new generation of communication technology using angle and distance, potentially replacing TDM, FDM or CDMA, for multiplexing. It is equivalent to wave packet compression by scaling of time at the receiver, converting path-dependent phase into distance-dependent shifts, and can multiply the capacity of physical channels. The effect was hitherto unsuspected in physics, appears to be responsible for both the cosmological acceleration and the Pioneer 10/11 anomaly, and is exhibited in audio data. This paper discusses how it may be exploited for instant, passive ranging of signal sources, for verification, rescue and navigation; incoherent aperture synthesis for smaller, yet more accurate radars; universal immunity to jamming or interference; and precision frequency scaling of ...