Activation of acyl phosphate monoesters by lanthanide ions towards biomimetic acylation. by Lisa Lynn Cameron

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Thesis (Ph.D.) -- University of Toronto, 2003.

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The Physical Object
Pagination115 leaves.
Number of Pages115
ID Numbers
Open LibraryOL20948876M
ISBN 100612846679

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Structurally, the phosphate group is connected to the acyl group by a single bond, and that the bond occurs between one of the oxygen atoms of the phosphate and the carbonyl carbon of the acyl group. The lanthanide (/ ˈ l æ n θ ə n aɪ d /) or lanthanoid (/ ˈ l æ n θ ə n ɔɪ d /) series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium.

These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare earth elements. The informal chemical symbol Ln. ―Lanthanide and Actinide Chemistry, Simon Cotton, Uppingham School, Uppingham, Rutland, UK.

Lanthanide and Actinide Chemistry is a one-volume account of the Lanthanides (including scandium and yttrium), the Actinides and the Transactinide elements, intended as an introductory treatment for undergraduate and postgraduate by: Comparisons of Phosphorothioate and Phosphate Monoester Transfer Reactions: Activation Parameters, Solvent Effects, and the Effect of Metal Ions Irina E.

Catrina and Alvan C. Hengge Journal of the American Chemical Society (10), The acidity constants of H2(AcP) and H2(AnP), where AcP2- = acetyl phosphate and AnP2- = acetonylphosphonate, as well as the stability constants of the complexes formed between Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, Cu2+, Zn2+, or Cd2+ and AcP2- or AnP2- were determined by potentiometric pH titrations in aqueous solution (25 °C; I = M, NaNO3).Cited by: THE SYNTHESIS AND PROPERTIES OF THE ACYL PHOSPHATES OF SOME HIGHER FATTY ACIDS BY ALBERT L.

I,EHn-INGER’C (1,2) on the activation of fatty acid oxidation by adenosinc t,riphosphate, a working hypothesis on the nature of this activation was elaborated. This hypothesis suggested Barium Monopalmityl Phosphate-Barium ions form an exceedingly.

Activation of Acyl Phosphate Monoesters by Lanthanide Ions: Enhanced Reactivity of Benzoyl Methyl Ph May Journal of the American Chemical Society Ronald Kluger.

Kinetics and Mechanistic Study of Hydrolysis of Adenosine Monophosphate Disodium Salt (AMPNa2) in Acidic and Alkaline Media Activation of acyl phosphate. monoesters by lanthanide ions. 4f orbitals (and the atoms in general) steadily contract across the lanthanide series.

Effective electron potential for the excited states of Ba {[Xe] 6s 4f} & La {[Xe] 6s 5d 4f} show a sudden change in the broadness & depth of the 4f "inner well". For Ba (Z = 56) 4f is File Size: KB. Lanthanide-mediated phosphoester hydrolysis and phosphate elimination from phosphopeptides{Nathan W.

Luedtke and Alanna Schepartz* Received (in Cambridge, MA, USA) 19th JulyAccepted 9th September First published as an Advance Article on the web 30th September DOI: /ba Lanthanide ions can mediate both.

Synthesis and Structural Characterization of Lanthanide-Containing Polyoxometalates by Amal Hamdy Ismail A thesis submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry Approved Dissertation Committee: Prof.

Ulrich Kortz (mentor, Jacobs University). The divalent first row transition metal ions (except for V 2+, Cr 2+ & Cu 2+) as well as Mg 2+ and the trivalent lanthanide ions.

Class III Exchange-rate constants are between 1 and 10 4 sec sec This class includes Be 2+, V 2+, Al 3+, Ga 3+ and several trivalent and several trivalent first-row transition metal ions.

Class IV Exchange rate File Size: KB. Extractions of five kinds of lanthanide metal ions by bis(2-ethylhexyl)phosphoric acid (DEHPA) with [1-Cnmethylimidazolium][PF 6](Cn = C 2, C 4) or [1-butylmethylpyridinium][PF 6] were carried out under various DEHPA and HNO 3 concentrations from 0 to 1 M and under different temperature conditions from to K.

These results were compared with those using the conventional organic Cited by: As the atomic number in the lanthanide series increases, the scission at the 5′-side is gradually promoted (the filled bars). On the other hand, the scission at the 3′-side is suppressed (the shaded ones).

As the result, the 5′/3′ ratio for each of the lanthanide ions monotonously increases Cited by: 6. neodymium and lanthanum; the phosphate portion of monazite contains small traces of other lanthanide ions and the only lanthanide that does not occur naturally is promethium, which is made artificially by nuclear reaction.

Bastnaesite, found in USA and Madagascar is a mixed fluorocarbonate MIIICO3F where M is La or the lanthanide metals.

It File Size: KB. The development of new proton-conducting materials that are cost effective and have high proton conductivity and water stability is very important in fuel cell technology.

Lanthanide-based metal–organic frameworks (MOFs) exhibit proton conduction properties but. The scissile phosphate of the substrate is displaced from its normal position by about 1 A when Eu3+ is bound and the presence of Eu3+ in the active site precludes the binding of the essential metal ion B.

CONCLUSIONS: The substantial, lanthanide-induced differences in metal-ion and substrate binding to KF exo account for the inhibition of this Cited by: The lifetime of emission from the excited state of the lanthanide ions falls in the range of microseconds (e.g.

Yb, Nd) to milliseconds (e.g. Eu and Tb). Such relatively long-lived emission is an attractive feature from an analytical viewpoint, as it allows the implementation of time-gating procedures so. Purchase The Chemistry of the Lanthanides - 1st Edition.

Print Book & E-Book. ISBNBook Edition: 1. ACTIVATION OF CARBOXYL GROUPS USING 2-MERCAPTOBENZOTHIAZOLE Introduction Activation of carboxyl group is one of the important steps in peptide synthesis. l5 This is usually done by converting the acids to azides, 20 mixed anhydrides, 25 acid halides, l8 File Size: KB.

Lanthanide-mediated phosphoester hydrolysis and phosphate elimination from phosphopeptides Nathan W. Luedtke and Alanna Schepartz* Department of Chemistry and Molecular, Cellular, and Developmental Biology, Yale University, New Haven, CT ~ Supplementary Information ~ I.

Reaction conditions, materials, and peptide synthesis II. As the program has shown, every lanthanide element forms a +3 oxidation state which is very stable to oxidation or reduction. In keep ing with its stability, this oxidation state is very easily made.

For example, the metals all dissolve readily in acid to form tri-positive File Size: KB. Wikimedia Commons has media related to Lanthanide compounds.

Subcategories. This category has the following 16 subcategories, out of 16 total. Pages in category "Lanthanide compounds" This category contains only the following page.

This list may not reflect recent changes. Lanthanide phosphates are known as slightly soluble salts with their solubility products ranging from to These phosphates can be obtained a) by precipitation from aqueous solutions of their salts using, for example, sodium or ammonium phosphates or b) by crystallization from boiling phosphoric acid solution.

Application of crystallization in highly acidic solution instead of Cited by: Ans: Lanthanide contraction: The regular decrease in the size of lanthanide ions from atomic num Cerium to 71, Lutetium to is known as lanthanide contraction.

It is due to greater effect of the increased nuclear charge than that of the screening effect. In lanthanide series with increasing atomic number there is a progressive decrease in theFile Size: 56KB. The paramagnetic behavior of lanthanide(III) ions is due to the presence of unpaired 4f electrons.

Since these 4f electrons are well shielded by the 5s25p6 octet, the magnetic susceptibility of a lanthanide(III) complex should indicate whether these 4 f electrons are affected by bond formation or not.

The magnetic moments of the present chelates. Synthesis of a Novel Acyl Phosphate Cross-linker and its Modification of Hemoglobin Elizabeth Wilson Master of Science Department of Chemistry University of Toronto Abstract Hemoglobin-based oxygen carriers (HBOCs) are of great interest for their potential as a Author: Elizabeth Wilson.

In the AP Pi structure, the tetrahedral phosphate participates in interactions with the two active-site zinc ions, the guanidino nitrogen atoms of Arg and two water molecules. The bidentate interaction of Arg with the phosphate oxygen atoms is pla-nar. The side-chain of Ser is clearly disordered, having two different conformations with.

Solution Chemistry of Other Lanthanide Oxidation States Ln(IV) Cerium is the only Ln 4+ with significant aqueous or coordination chemistry. E° (Ce 4+ (aq)/Ce 3+ (aq)) = V (others est.

„ V) prepared by the action of a strong oxidizing agent, e.g. S 2 O 8 2- on Ce 3+ (aq) widely used as an oxidant itself: e.g. quantitative analysis. Extraction of Lanthanides from Monazite sand: The technique used for extraction of lanthanides from monazite sand comprises of the steps that have been illustrated in flow sheet.

Flow sheet: Extraction of lanthanide from monazite sand. Individual lanthanides are estranged by an appropriate physical technique. The anhydrous fluorides and /5(K). Are lanthanide ions like Nd3+ hard or soft acids. I'm learning about HSAB theory in inorganic chemistry class at the moment.

Couldn't find any resources or research that discuss the hard or soft nature of lanthanide metals. I was wondering if anyone was aware of if this research has been conducted or not.

The reason I ask is because I'm. In this work, the effect of the substituent at the α or β position in dialkylphosphinic acids on the extraction of trivalent lanthanide ions was investigated using experimental and theoretical methods.

Five dialkylphosphinic acids were synthesized. Their extractions of. Specific features of the textures (the preferred orientation of the nanometer building blocks) of the cationic and anionic components of the structures of phosphates forming in the Ln2O3-P2O5 systems (Ln = Er-Lu) have been studied.

Nanostructuring upon the formation of phosphates is determined by two oppositely directed processes of fragmentation of corresponding infinite cationic Cited by: 1.

The history of the rare earths has entered its third century; trans uranium elements are now a half century old. Both the lanthanide and actinide ele­ ments, 30 elements altogether, are f elements, meaninj that their metallic 2 1 1 electronic configurations are typically 6s 5d 4f" and 7s 6d 5f" : G.

Meyer. Lanthanides as substitutes for calcium ions in the activation of plant α-type phospholipase D. Dressler L, Golbik R, Ulbrich-Hofmann R. Most types of phospholipase D (PLD) from plants contain a C2 domain and are activated by Ca(2+) ions. In this study, other metal ions such as Mg(2+), La(3+), Ce(3+), Tb(3+) and Y(3+) were examined as effectors Cited by: 7.

Williams R.J.P. () The chemistry of lanthanide ions in solution and in biological systems. In: Topics in Inorganic and Physical Chemistry. Structure and Bonding, vol Cited by:   Enzymes provide enormous rate enhancements, unmatched by any other type of catalyst.

The stabilization of high-energy states along the reaction coordinate is the crux of the catalytic power of enzymes. We report the atomic-resolution structure of a high-energy reaction intermediate stabilized in the active site of an enzyme.

Crystallization of phosphorylated β-phosphoglucomutase in the. Transition state analysis and requirement of Asp general acid/basecatalyst for full activation of dual-specificity phosphatase MKP3 byextracellular regulated kinase.

BIOCHEMISTRY,Rishavy, M., Hengge, A.C, Cleland, W., (). Lanthanide catalyzed cyclization of uridine 3 ‘-p-nitrophenyl phosphate. A chiral derivatizing agent (CDA) also known as a chiral resolving reagent, is a chiral auxiliary used to convert a mixture of enantiomers into diastereomers in order to analyze the quantities of each enantiomer present within the mix.

Analysis can be conducted by spectroscopy or by chromatography. The use of chiral derivatizing agents has declined with the popularization of chiral HPLC. Activation of Enzymes. III pressed through muslin, yielding an extract of about ml. The residue may be profitably reextracted and worked up further, if desired.

To the fluid extract is added toluene, 25 ml., and, after being well shaken, the mixture is allowed to stand in a refrigerator for 12 hours. Lignocellulolytic enzymes have been extensively studied due to their potential for industrial applications such as food, textile, pharmaceutical, paper, and, more recently, energy.

The influence of metal ions, chemical agents, and organic compounds on these enzyme activities are addressed in this chapter, based on data available in the scientific by: NMR Shift Reagents.

Certain lanthanide compounds form complexes with molecules featuring -O- or -N.Lanthanide Organometallics: Organometallic Chemistry. Organolanthanide chemistry is not as extensive as organotransition metal chemistry,; Currently receiving a lot of attention, especially in C-H Bond Activation studies; Primarily ionic in their bonding Ð contracted nature of the 4f valence orbitals ; Lanthanides cannot act as p-bases Þ Ln-CO compounds are not stable.

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