Gaseous dipeptide complexes with metal ions by electrospray ionization and tandem mass spectrometry

Electrospray ionization (ESI) and tandem mass spectrometry have been used to investigate the gas-phase interactions of five metal ions and seven dipeptides. For silver ion, two complexes ([M+Ag](+) and [2M+Ag](+)) were obtained as well as the one complex ([2M+Met-H](+)) for transition-metal ions. Upon collision activation, there is an obvious difference in MS/MS data between metal ion complex and the protonated molecule. The fragment pathway of each complex is related to the structures of dipeptide and the nature of metal ion which suggest that there are several interaction between the metal ions and dipeptides in gas phase.

Novel, covalently bonded hybrid materials of europium (terbium) complexes with silica

New kinds of hybrid materials containing covalently bonded Eu3+ (Tb3+) bipyridine complexes in a silica network have been prepared and their luminescence properties reported.

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

Investigation of metalloporphyrins and their imidazole complexes using electrospray ionization mass spectrometry

Three compounds of metalloporphyrins were studied using electrospray ionization mass spectrometry. The bonding power between substitutional phenyl and porphyrin cycle and the coordinate conditions of metalloporphyrins with imidazole were discussed. The experimental result indicated that the bonding power between substitutional phenyl and porphyrin cycle in metalloporphyrins became weak from Mn, Fe to Co. The complexes abundances formed by metallophorphyrin with imidazole were stronger with the increase of the ligand concentration. At the same ligand concentration, the abundance of the complexes was intensified gradually and the stability of the ligands was become stronger from Mn, Fe to Co.

Preparation and luminescence properties of lanthanide complexes and their silica-based composites

Binary complexes of europium and terbium with N-propyl-4-carboxyphthalimide (NP) were prepared and characterized. The luminescence behaviors of the lanthanide complexes as well as their doped silica-based composites were investigated by fluorescence spectra. The results indicated that the lanthanide complexes showed fewer emission lines and slightly lower intensities in silica matrix than that of corresponding pure complexes. The lifetimes of the lanthanide complexes became longer when they were incorporated in silica matrix. (C) 2001 Elsevier Science B.V. All rights reserved.

Syntheses and crystal structures of novel di- and trinuclear rhodium complexes bridged by pyrazine

Never di- and trinuclear Rh complexes, [Rh-2(PPh3)(4)(H)(4)(Me2CO)(2)(mu -pyz)](ClO4)(2). EtOH and [Rh-3(PPh3),(mu -pyz)(3)](ClO4)(3). EtOH were selectively isolated from the reaction of [Rh(PPh3)(2)(H)(2)(Me2Co)(EtOH)]ClO4 with pyrazine (pyz) in Me2CO and THF, respectively. Their structures were crystallographically characterized.

Synthesis and luminescence properties of ternary europium complexes in titania matrix in the presence of dimethylformamide by a sol-gel process

In-situ synthesis of ternary europium complex with thenoyltrifluoacetone (TTA) and 1,10-phenanthroline (phen) in titania matrix in the presence of dimethylformamide (DMF) by a sol-gel process was described, which was confirmed by the luminescence excitation spectra and infrared spectra. The titania gel that contains europium complex exhibits Eu3+ characteristic emission bands and presents a longer fluorescence lifetime than the pure complexes dissolved in ethanol solution. The concentration effect on the luminescence intensity was also investigated.

New development of organolanthanide complexes containing chalcogenide ligands

This article is to present and outline new approaches to chalcogen coordination chemistry from the organolanthanides point of view.

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

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

Binuclear lanthanide complexes as catalysts for the hydrolysis of double-stranded DNA

The efficient cleavage of plasmid DNA ( pCAT) by binuclear lanthanide complexes was investigated. At 37 degrees C and neutral pH, both Ho23+L and Er23+L promoted 100% conversion of supercoiled plasmid to the nicked circular form and linear form in 1 h. The corresponding saturation kinetics curve of cleavage of pCAT plasmid by binuclear lanthanide complexes showed the expected increase with catalyst concentration. (C) 1999 Elsevier Science S.A. All rights reserved.

Synthesis, structure characterization of the complexes of beta-alkoxycarbonylethyltin trichlorides with Schiff base ligands

Thirty - two title complexes (ROCOCHRCH2SnCl3)-C-1 . (2 - HOC6H4CH = NC6H4 - X) (R = Me, Et, n - Bu; R-1 = H, Me; X = H,4' - Cl, 3' - Pr, 3' - OH, 3', 4' - Cl-2, 4' - OMe) were synthesized and characterized by elemental analysis,UV - vis, IR, H-1 NMR. The crystal structure of n - BuOCOCH2CH2SnCl3 . (2 - HOC6H4CH - NC6H4OMe - 4') were determined by the X - ray diffraction analysis, The crystal belongs to monoclinic system, with a = 1.4661 (3)nm, b = 0.9307 (2)nm, c = 1.7888 (4)nm, beta = 94.04 (3)degrees, V = 2.4348nm(3), D-c = 1.581mg/m(3), Z = 4, F(000) = 1160, mu = 1.405mm(-1), R = 0.0354, R-w = 0,0486, space group: P2(1)/c. The complexes exist as a discrete monomer. The tin atom has a distorted octahedral geometry due to intramolecular coordination of the carbonyl oxygen and the phenolic oxygen of the Schiff base ligands, The coordination number of tin atom is 6.

Cleavage of nucleotides by Ce4+ and the lanthanide metal complexes

The cleavage of adenosine-5'-monophosphate (5'-AMP) and guanosine-5'-monophosphate (S-GMP) by Ce4+ and lanthanide complex of 2-carboxyethylgermanium sesquioxide (Ge-132) in acidic and near neutral conditions was investigated by NMR, HPLC and measuring the liberated inorganic phosphate at 37 degrees C and 50 degrees C, The results showed that 5'-GMP and 5'-AMP was converted to guanine (G), 5'-monophosphate (depurination of 5'-GMP), ribose (depurination and dephosphorylation of 5'-GMP), phosphate and adenine (A), 5'-monophosphate (depurination of 5'-AMP), ribose (depurination and dephosphorylation of 5'-AMP), phosphate respectively by Ce4+. In presence of lanthanide complexes, 5'-GMP and 5'-AMP were converted to guanosine (Guo) and phosphate and adenosine (Ado) and phosphate respectively. The mechanism of cleaving 5'-GMP and 5'-AMP is hydrolytic scission.

Studies of non-covalent protein complexes by MALDI methods

Several specific non-covalent protein complexes were successfully observed by matrix assisted desorption ionization mass spectrometry(MALDI MS). The methods described in this paper include the matrixes use of sinapinic acid(SA) and 6-aza-2-thiothymine (ATT) in neutral pH solution, as well as the improvement of two-layer sample preparation method to achieve a high sensitivity detection of stable non-covalent complexes, Myoglobin-heme complex was found simultaneously with the sinapinic acid matrix in the various pH solution(pH=2 or pH=5), The RNase S complex showed a striking intensity at the first shot, which was decreased with more laser shots. Most importantly, the observation of specific non-covalent complex in the brome mosaic virus(BMV) coat proteins would open up a new possibility to investigate the assembly and disassembly of viral capsids.

Cleavage of nucleotides by lanthanide metal complexes

The present work revealed that the praseodymium( II ) complex of 2-carboxyethylgermanium sesquioxide (Ge-132) promotes the hydrolysis of the phosphodiester linkages of 3',5'-cyclic adenosine monophosphate (cAMP), 3' , 5'-cyclic deoxyadenosine monophosphate (dcAMP), 5'-adenosine monophosphate(5'-AMP) and 5'-deoxyadenosine monophosphate (5'-dAMP) under mild conditions. Both cAMP and dcAMP were hydrolyzed site-specifically, yielding predominantly 3'-monophosphates, the main products of the cleavage of 5'-AMP and 5'-dAMP included adenosine (Ado). deoxyadenosine (dAdo) and free phosphates respectively. A hydrolytic mechanism was proposed for cAMP, dcAMP, 5'-AMP and 5'-dAMP.