Search results for "DIIS"
showing 10 items of 135 documents
Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganatio…
2008
With the aim of introducing the diisopropylamide [NiPr(2)](-) ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na(2)Mn(2) (mu-H)(2){N(iPr)(2)}(4)]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganati…
Reversed Enantioselectivity of Diisopropyl Fluorophosphatase against Organophosphorus Nerve Agents by Rational Design
2009
Diisopropyl fluorophosphatase (DFPase) from Loligo vulgaris is an efficient and robust biocatalyst for the hydrolysis of a range of highly toxic organophosphorus compounds including the nerve agents sarin, soman, and cyclosarin. In contrast to the substrate diisopropyl fluorophosphate (DFP) the nerve agents possess an asymmetric phosphorus atom, which leads to pairs of enantiomers that display markedly different toxicities. Wild-type DFPase prefers the less toxic stereoisomers of the substrates which leads to slower detoxification despite rapid hydrolysis. Enzyme engineering efforts based on rational design yielded two quadruple enzyme mutants with reversed enantioselectivity and overall en…
Determination of selected phthalates by gas chromatography–mass spectrometry in mural paintings from Palermo (Italy)
2013
Abstract Phthalate esters for decades, and probably even now, were used as softeners in water-based paintings. In general, these compounds are dangerous owing to their carcinogenicity and reproductive effects. Phthalates are not chemically but only physically bound to the matrices, hence, they may be leached into the environment and are ubiquitously found in environmental matrices. Considering that, construction is one of most important fields in Europe, and probably worldwide, with respect to its economic, technological and environmental impact. In the present work the phthalate esters content of several mural paintings was evaluated by gas chromatography–mass spectrometry (GC-MS). Because…
Acetylcholinesterase-Capped Mesoporous Silica Nanoparticles That Open in the Presence of Diisopropylfluorophosphate (a Sarin or Soman Simulant)
2016
Mesoporous silica nanoparticles loaded with rhodamine B and capped with acetylcholinesterase are able to be selectively opened and deliver their cargo in the presence of nerve agent simulant diisopropyl fluorophosphate (DFP).
The Chemistry of [1,2,3]Triazolo[1,5- a] pyridines
2003
The reactivity of [1,2,3]triazolo[1,5-a]pyridines 1 is described. Triazolopyridines react with electrophiles in two contrasting ways, giving 3-substituted triazolopyridines 2, or products 3, resulting from triazolo ring opening with loss of molecular nitrogen. The triazolopyridines can be lithiated at -40 degrees C by lithium diisopropylamide in ether giving regiospecifically the 7-lithio derivative. Bromotriazolopyridines have activation towards nucleophilic substitution at position 5 and 7, and benzenoid inertness at position 6. The parent compound 1a is easily hydrogenated giving tetrahydrotriazolopyridine 11a in high yield; when the triazolopyridines have substituents, the hydrogenation…
Influence of the polymerization step alone on oxygen affinity and cooperativity during production of hyperpolymers from native hemoglobins with cross…
1994
The aim of this study was to find out how the polymerization per se changes oxygen affinity (P50) and cooperativity (n50) of various soluble huge hyperpolymers prepared from native hemoglobins by crosslinking. Increase of cooperativity would be expected considering natural hemoglobin networks. Those hyperpolymers with molecular weights of some 10(6) g/mol are candidates for artificial oxygen-carrying blood additives rather than volume substitutes. Human and bovine hemoglobin reacted with several crosslinkers (2,5-diisothiocyanatobenzenesulfonate (DIBS); 4,4'-diisothiocyanatostilbene-2, 2'-disulfonate (DIDS); 1,3-butadiene diepoxide (BUDE); glutaraldehyde (GDA)) in concentrated (case 1) and …
Detection of proteolytic (C 3-cleaving) activity on mouse mastocytoma (P815) cells and other mouse cell lines by formation of cell contact with C 3-c…
1979
Mouse mastocytoma cells (P 815) formed rosettes with normal mouse spleen lymphocytes which had been coated with uncleaved human C 3; this interaction was clearly dependent on the amount of C 3. Lymphocytes treated with C 3 b or buffer alone were ineffective. Formation of cell contact could be inhibited by the presence of protease inhibitors such as diisopropyl fluorophosphate, phenyl methyl sulfonyl fluoride and tosyllysyl chloromethyl ketone. Seve n out of 13 different cell lines behaved like P 815 cells. The results strongly suggested that a proteolytic activity on mouse tumor cells led to a cooperation with uncleaved C 3 on a carrier cell to connect these two cells. We interpreted these …
A Chromogenic Probe for the Selective Recognition of Sarin and Soman Mimic DFP
2014
The synthesis, characterization and sensing features of a novel probe 1 for the selective chromogenic recognition of diisopropylfluorophosphate (DFP), a sarin and soman mimic, in 99:1 (v/ v) water/acetonitrile and in the gas phase is reported. Colour modulation is based on the combined reaction of phosphorylation of 1 and fluoride-induced hydrolysis of a silyl ether moiety. As fluoride is a specific reaction product of the reaction between DFP and the OH group, the probe shows a selective colour modulation in the presence of this chemical. Other nerve agent simulants, certain anions, oxidant species and other organophosphorous compounds were unable to induce colour changes in 1. This is one…
In vitro and in vivo efficacy of PEGylated diisopropyl fluorophosphatase (DFPase)
2011
Highly toxic organophosphorus compounds that irreversibly inhibit the enzyme acetycholinesterase (AChE), including nerve agents like tabun, sarin, or soman, still pose a credible threat to civilian populations and military personnel. New therapeutics that can be used as a pretreatment or after poisoning with these compounds, complementing existing treatment schemes such as the use of atropine and AChE reactivating oximes, are currently the subject of intense research. A prominent role among potential candidates is taken by enzymes that can detoxify nerve agents by hydrolysis. Diisopropyl fluorophosphatase (DFPase) from the squid Loligo vulgaris is known to effectively hydrolyze DFP and the …