Synthesis and Biological Characterization of Argyrin F <<>>

Written by Leila Bülow, Irina Nickeleit, Anna-Katharina Girbig, Tobias Brodmann, Andreas Rentsch, Ulrike Eggert, Florenz Sasse, Heinrich Steinmetz, Ronald Frank, Teresa Carlomagno, Nisar P. Malek, Markus Kalesse on March 31, 2010 – 12:10 pm -

Argyrin F unfolds its cheering antitumor enterprise twice: Earliest through stabilization of the tumor suppressor protein p27 and number two by vascular damage <<>>

Posted in biochem, chemistry, medicine | Comments Off

Site-Selective Ser-Hydrolase Labelling with a Luminescent Organometallic NCN-Platinum Complex <<>>

Written by Birgit Wieczorek, Bart Lemcke, Harm P. Dijkstra, Maarten R. Egmond, Robertus J. M. Klein Gebbink, Gerard van Koten on March 31, 2010 – 12:06 pm -

The synthesis, spectroscopic properties and protein-binding studies of a unconventional luminescent organometallic NCN-platinum complex are described. The luminescent organometallic complex was linked to a serine hydrolase reactive phosphonate clique by means of click chemistry, and was exploited in serine hydrolase specific-binding studies using gel electrophoresis. The NCN-platinum protein label was originate to be a staunch dye with absorbance and emission maxima between 374-380 and 482-493 nm, respectively, and quantum yields intermediary 0.04 and 0.15 <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Self-Assembled Lanthanide Salicylaldimines with a Second to none in harmony Coordination Standard operating procedure <<>>

Written by Ma[lstrok]gorzata T. Kaczmarek, Maciej Kubicki, Anna Mondry, Rafa[lstrok] Janicki, Wanda Radecka-Paryzek on March 31, 2010 – 12:06 pm -

New lanthanide salicylaldimine complexes of the prescription [Ln(H2L)3(NO3)3](H2L), where Ln = La3+ (1), Nd3+ (2), Eu3+ (3), Gd3+ (4), Ho3+ (5), Er3+ (6), Tb3+ (7) or Yb3+ (8), and H2L = N,N[prime]-bis(salicylidene)-4-methyl-1,3-phenylenediamine, were formed in a self-assembly organize involving the lanthanide template-induced one-step [2+1] Schiff post condensation counteraction negotiator salicylaldehyde and 4-methyl-1,3-phenylenediamine. The unconventional coordination model of salen-type ligands in these complexes, in which the three potentially tetradentate N2O2 salicylaldimines dinner as undeprotonated, monodentate, exclusively O-donor ligands without involving the nitrogen atoms in the coordination environment, was proved by single-crystal X-ray diffraction examination and correlated with spectroscopic characterization. In this species with the nine-coordinate distorted tricapped trigonal prism geometry, the nitrates act as bidentate chelators occupying six coordination sites and leaving the remaining sites elbow for salicylaldimine ligands formed in situ in the templet get ready. The additional salicylaldimine molecule acts as a caller for the salicylaldimine complex horde and stabilizes the all-embracing self-assembled supramolecular network <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Synthesis, Crystal Structures, and Charismatic Properties of MnII, CoII, and ZnII Coordination Polymers Containing 1,2,4,5-Benzenetetracarboxylic Acid and 4,4[prime]-Azobispyridine <<>>

Written by Li-Min Zhao, Huan-Huan Li, Ying Wu, Shi-Yuan Zhang, Zhen-Jie Zhang, Wei Shi, Peng Cheng, Dai-Zheng Liao, Shi-Ping Yan on March 31, 2010 – 12:06 pm -

Manganese(II), cobalt(II), and zinc(II) coordination polymers, {[Mn(H2btec)(azopy)(H2O)2]·(azopy)}n (1), {[Co(H2btec)(azopy)(H2O)2]·(azopy)}n (2), and {[Zn2.5(btec)(azopy)([mu]3-OH)(H2O)]·H2O}n (3) (H4btec = 1,2,4,5-benzenetetracarboxylic acid; azopy = 4,4[prime]-azobispyridine), were synthesized by ahydrothermal method and characterized by single-crystal X-ray diffraction, primordial analysis, and authorities X-ray diffraction. Compounds 1 and 2 are isomorphic and crystallize in the triclinic space platoon P, exhibiting a 2D grid framework bridged by two types of ligands. Increase 3 also crystallizes in the triclinic lacuna band P and take an fascinating 3D coordination framework with an unprecedented dodecadentate coordination trend and a together {416.510.618.7}{44.5.6}2 topological form. The paradigm topology of 3 has not been encountered in metal-organic framework chemistry, which has been deposited in the Reticular Chemistry Design Resource under the aegis the name zim net. Arresting studies pretension that there are antiferromagnetic interactions in both 1 and 2. The cyclic voltammograms of 1-3 in the solid stage were also obtained <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Dicarba-closo-dodecaboranes with One and Two Ethynyl Groups Bonded to Boron <<>>

Written by Alexander Himmelspach, Maik Finze on March 31, 2010 – 12:06 pm -

The diethynyldicarba-closo-dodecaboranes 1,2-R2-9,12-(HCC)2-closo-1,2-C2B10H8 [R = H (1a), Me (2a)] and 9,10-(HCC)2-closo-1,7-C2B10H10 (3a) were obtained by Pd-catalyzed Kumada-type cross-coupling reactions of the corresponding diiodinated dicarba-closo-dodecaboranes withMe3SiCCMgBr followed by desilylation of the trimethylsilylalkynyl-substituted clusters. In addition, the related {closo-C2B10} derivatives with one ethynyl party 1,2-R-9-HCC-closo-1,2-C2B10H9 [R = H (4a), Me (5a)], 9-HCC-closo-1,7-C2B10H11 (6a), and 2-HCC-closo-1,12-C2B10H11 (7a) were synthesized and their spectroscopic properties were compared to those of the diethynyl-substituted {closo-C2B10} clusters. The ethynyl- and trimethylsilylalkynyl-functionalized dicarba-closo-dodecaboranes were characterized by elemental analysis, collection spectrometry, as luckily as by multinuclear NMR, IR, and Raman spectroscopy. The job of the NMR spectroscopic chemical shifts and the IR and Raman bands is supported by supposititious values derived from density effective calculations. The crystal structures of 9,12-(HCC)2-closo-1,2-C2B10H10 (1a), 9,10-(HCC)2-closo-1,7-C2B10H10 (3a), and 1,2-Me-9,12-(Me3SiCC)2-closo-1,2-C2B10H8 (2b) were purposeful by single-crystal X-ray diffraction. Selected experimental bond properties are compared to bond lengths and angles purposeful at the B3LYP/6-311++G(d,p) unvarying of theory <<>>

Posted in biochem, chemistry, inorganic | Comments Off

A Structural Probe of Trivalent and Divalent Rare Clay Thiocyanate Complexes Synthesised by Redox Transmetallation <<>>

Written by Jacinta M. Bakker, Glen B. Deacon, Craig M. Forsyth, Peter C. Junk, Michal Wiecko on March 31, 2010 – 12:06 pm -

A broad series of reactive trivalent and divalent rare world thiocyanate complexes with 1,2-dimethoxyethane (dme), tetrahydrofuran (thf) and acetonitrile namely [RE(NCS)3(dme)3] [RE = La (1a), Nd (1b)], [RE(NCS)3(dme)2([mu]-dme)0.5]2 [RE = Dy (1d), Er (1e)], [RE(NCS)3(thf)4]2 [RE = Y (3a), La (3b), Nd (3c), Sm (3d), Dy (3e), Ho (3f)], [Ca(NCS)2(dme)3] [rac-(4a)], [RE(NCS)2(dme)3] (RE = Sm (rac-4b), Eu (rac-4c), [Ca(Yb)(NCS)2(NCMe)5]·NCMe [Ca (6a), Yb (6b)], and [Eu(NCS)2(thf)4]2 (7) beget been ready-to-serve in special-occasion to exhilarated give way by redox transmetallation agent rare blue planet metals and the commercially handy Hg(SCN)2. In addition [Eu(NCS)3(dme)2([mu]-dme)0.5]2 (1c) and [Yb(NCS)3(dme)2] (1f) experience been treated by oxidation of rac-4c and [Yb(NCS)2(thf)2], respectively, with Hg(SCN)2 in dme. Crystallisation of 1e from dme/diglyme (diglyme = bis(2-methoxyethyl) ether) and thf yields [Er(NCS)3(diglyme)(dme)] (2) and [Er(NCS)3(thf)4]2 (3g), respectively, and prolonged storage of rac-4a in keen dme gave [Ca(NCS)2(dme)2(H2O)] (5). All live speedy hydrolysis on jeopardy to air. Two structural breaks are observed for [RE(NCS)3(dme)n] complexes, all of which have in the offing solely RE-NCS binding. Compounds 1a,b are nine-coordinate monomers that be separate in the structure (T or Y) of the RE(NCS)3 moiety, 1c-e are eight systemize dinuclear complexes being bridged by a single [eta]1:[eta]1-(O,O[prime])-dme and 1f is a seven equivalent monomer. 2 is an eight rank monomer with, unusually for the present complexes, a facial RE(NCS)3 array. By distinction 3a-g are all dimeric, eight correlative complexes with two atypical RE-NCS-RE bridges. The RE-S bonds are awfully stupid and put to shame sparse change of pace with RE3+ radius, and Er-S of 3g increases by 0.18 Å liaison 123 K and accommodation temperature), foreshadowing a transmute to a seven parallel monomer with [Yb(NCS)3(thf)4]. Monomeric eight coordination with transoid (N-RE-N [ap] 149°) SCN-RE-NCS bonding is observed in rac-4a-c and [Lambda]-4c, whilst 5 is a seven-coordinate monomer with a cis-Ca(NCS)2 array. Apart crystals of 6,a,b carry seven-coordinate, pentagonal bipyramidal monomers with trans-NCS ligands, whereas 7 is dimeric with two Eu-NCS-Eu bridging ligands and seven coordination for Eu <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Structural and Spectroscopic Characterisation of Linearly Coordinated Gold(I) Tribenzylphosphane Complexes <<>>

Written by Eric W. Ainscough, Graham A. Bowmaker, Andrew M. Brodie, Graham H. Freeman, John V. Hanna, Peter C. Healy, Ward T. Robinson, Brian W. Skelton, Mark E. Smith, Alexandre N. Sobolev, Allan H. White on March 30, 2010 – 8:54 am -

The 1:1 tribenzylphosphane (PBn3) complexes of gold(I)[(Bn3P)AuX] (X = Cl and Br) must been synthesised, and their structures were ascertained by single-crystal X-ray crystallography. The compounds are isomorphous, neutral molecules with linearly coordinated P-Au-X arrays. Each structure contains three individualistic [(Bn3P)AuX] entities untruthfulness on the three threefold axes of space squad P3c1. The approach manacles lengths are Au-Cl 2.302(8), Au-P 2.227(11) Å for the chloride and Au-Br 2.404(10), Au-P 2.229(4) Å for the bromide. These set off with the 1:1 adducts in days of old reported for copper(I), which exact the make up [Cu(PBn3)2][CuX2]. The 1:2 AuX:PBn3 compounds that give birth to been synthesised are formulated as [Au(PBn3)2]X·nH2O (X = Cl, n = 1 or 2; X = I and BF4, n = 0). Single-crystal X-ray structures register that linearly two-coordinate centrosymmetric [Au(PBn3)2]+ arrays are initiate in [Au(PBn3)2]Cl·H2O and [Au(PBn3)2]BF4 with Au-P pact lengths of 2.2988(7) and 2.3016(7) Å for the chloride and 2.2975(7) Å for the tetrafluoroborate. [nu](AuX) bands in the far-IR spectra of [(Bn3P)AuX] are assigned at 320 and 227 cm-1 for X = Cl and X = Br, severally. The 31P CP MAS NMR spectra of [(Bn3P)AuX] (X = Cl, Br) and [Au(PBn3)2]X (X = Cl·H2O, Cl·2H2O, I, BF4) are reported, and the word of 2J(PP) coupling in the spectrum of [Au(PBn3)2]Cl·2H2O is conforming with the self-assurance in this complex of noncentrosymmetric cations in which the two phosphorus atoms are inequivalent <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Oxidomolybdenum(IV), -(V), -(VI) Complexes with Significance to Molybdenum Enzymes: Oxygen Atom Transfer, Redox Chemistry and EPR Spectroscopy <<>>

Written by Katja Heinze, Andreas Fischer on March 26, 2010 – 2:03 pm -

The cis-dioxidomolybdenum(VI) complex Mo(NN[prime])2O2 (1) [(NN[prime]) = N-(4-hydroxyphenyl)-2-pyrrolatocarbaldimine] transfers one oxygen atom to phosphanes PMenPh3-n (n = 0-3) to confer quantitatively the relevant phosphane oxides OPMenPh3-n (OAT, oxygen atom transfer). The kinetics of these OAT reactions has been investigated spectrophotometrically. When contribution supererogation PMenPh3-n (n = 1-3), oxido(phoshane)molybdenum(IV) complexes Mo(NN[prime])2O(PMenPh3-n) 5a-5c are cut off and characterized by multinuclear NMR spectroscopy (1H, 13C, 31P, 15N), IR spectroscopy, UV/Vis spectroscopy and store spectrometry. The redox chemistry of the molybdenum(IV) complexes 5a-5c and of molybdenum(VI) complex 1 has been probed by preparative one-electron oxidation and reduction, respectively, in emulsion with EPR spectroscopy under strictly anhydrous conditions. The reactivity of the resulting MoV species (ligand substitution, protonation, silyation) has been investigated to pen support inconsiderable onto the biomimetic catalytic rotate of OAT from open-handedly to substrates in bloc with two coupled electron proton carry reactions (CEPT) <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Anionic d8 Alkyl Hydrides - Eclectic Founding and Reactivity of Anionic cis-PtII Methyl Hydride <<>>

Written by Elena Poverenov, Mark A. Iron, Mark Gandelman, Yehoshoa Ben-David, David Milstein on March 26, 2010 – 2:03 pm -

The pincer-type complexes [(PCN)PtR] {R = H, 2; Me, 4; PCN = C6H4[CH2P(tBu)2](CH2)2N(CH3)2} proceed with MeLi or Et3BHNa, to announce anionic cis-Pt(Me)H complexes [(PCN*)Pt(H)(Me)]-Li+ (Me trans to P; PCN* denotes the PCN ligand in which the amine arm is not coordinated) and [(PCN*)Pt(Me)(H)]-Na+ (H trans to P). Not the isomer in which the entering nucleophile is situated trans to the phosphane ligand is formed. These elementary d8 anionic alkyl hydride complexes were fully characterized spectroscopically. The hemilabile PCN ligand allows for reversible de-coordination of the amine arm, thereby providing a fine deliberate of stability vs. reactivity. Supposititious calculations on copy systems disclose a concerted mechanism in which the nucleophilic condemn and the amine dissociation take place concurrently. The (unobserved) methane reductive elimination from the enduring anionic methyl hydride complex [(PCN*)Pt(Me)(H)]-Li+ (3) is thermodynamically and kinetically unfavorable, as indicated by DFT. This complex reacts with electrophiles, such as tap water and methyl iodide, to yield exclusively methane and the corresponding organometallic product (either 2 or 4). This reactivity was also accessory examined by DFT <<>>

Posted in biochem, chemistry, inorganic | Comments Off

Authentication of Potent and Picky Altruist Carbonic Anhydrase VII (hCA VII) Inhibitors <<>>

Written by Rosaria Gitto, Stefano Agnello, Stefania Ferro, Daniela Vullo, Claudiu T. Supuran, Alba Chimirri on March 26, 2010 – 2:03 pm -

Guarding the cloudy matter: This tract reports the recognition of sulfonamide derivatives as carbonic anhydrase inhibitors that selectively act against the hCA VII over the hCA II isoform. These compounds represent potentially utilitarian prospect structures for the what is more happening of neuroprotective agents targeting the hCA VII isoform <<>>

Posted in biochem, chemistry, medicine | Comments Off
RSS