Mechanistic investigation on the oxidation of ampicillin drug by diperiodatoargentate (III) in aqueous alkaline medium

The kinetics of oxidation of antibiotic drug, ampicillin (AMP) by diperiodatoargentate (III) (DPA) in alkaline medium at a constant ionic strength of 0.25‐mol dm^?3 was studied spectrophotometrically. The reaction between DPA and AMP in alkaline medium exhibits 1:2 stoichiometry (AMP:DPA). The reaction is of first order in [DPA] and has less than unit order in both [AMP] and [alkali]. Added periodate retarded the rate of reaction and intervention of free radicals was observed in the reaction. The oxidation reaction in alkaline medium has been shown to proceed via a DPA–AMP complex, which decomposes slowly in a rate‐determining step followed by other fast steps to give the products. The main products were identified by spot test, IR and NMR studies. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed and thermodynamic quantities were also determined. Copyright © 2008 John Wiley & Sons, Ltd.     

Ru(III), Os(VIII), Pd(II) and Pt(IV) catalysed oxidation of glycyl–glycine by sodium N‐chloro‐p‐toluenesulfonamide: comparative mechanistic aspects and kinetic modelling

The Ru(III)/Os(VIII)/Pd(II)/Pt(IV)‐catalysed kinetics of oxidation of glycyl–glycine (Gly‐Gly) by sodium N‐chloro‐p‐ toluenesulfonamide (chloramine‐T; CAT) in NaOH medium has been investigated at 308 K. The stoichiometry and oxidation products in each case were found to be the same but their kinetic patterns observed are different. Under comparable experimental conditions, the oxidation‐kinetics and mechanistic behaviour of Gly‐Gly with CAT in NaOH medium is different for each catalyst and obeys the underlying rate laws:

• Rate = k [CAT]_t [Gly‐Gly]⁰ [Ru(III)][OH^?]^x
• Rate = k [CAT]_t[Gly‐Gly]^x [Os(VIII)]^y[OH^?]^z
• Rate = k [CAT]_t[Gly‐Gly]^x [Pd(II)][OH^?]^y
• Rate = k [CAT]_t[Gly‐Gly]⁰ [Pt(IV)]^x[OH^?]^y

Here, and x, y, z < 1 in all the cases. The anion of CAT, CH₃C₆H₄SO₂NCl^?, has been postulated as the common reactive oxidising species in all the cases. Under comparable experimental conditions, the relative ability of these catalysts towards oxidation of Gly‐Gly by CAT are in the order: Os(VIII) > Ru(III) > Pt(IV) > Pd(II). This trend may be attributed to the different d‐electronic configuration of the catalysts. Further, the rates of oxidation of all the four catalysed reactions have been compared with uncatalysed reactions, under identical experimental conditions. It was found that the catalysed reaction rates are 7‐ to 24‐fold faster. Based on the observed experimental results, detailed mechanistic interpretation and the related kinetic modelling have been worked out for each catalyst. Copyright © 2008 John Wiley & Sons, Ltd.     

Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach

The kinetics of oxidation of methylxanthine drug, theophylline (TP), by diperiodatocuprate(III) (DPC) has been investigated in the absence and presence of ruthenium(III) (Ru(III)) as homogeneous catalyst in alkaline medium at a constant ionic strength of 0.21 mol dm^?3 spectrophotometrically. The reaction exhibits 1:4 stoichiometry ([TP] : [DPC]) in both the cases. The order of the reaction with respect to [DPC] was unity, while the order with respect to [TP] was less than unity over the concentration range studied in both the cases. The rate was increased with an increase in [OH^?] and decreased with an increase in [IO₄^?]. The order with respect to [Ru(III)] was unity. The ionic strength and dielectic constant of the medium did not affect the rate significantly. The main product 1‐methyl‐(3‐N‐formyl)‐2,4‐purinodione was identified by spot tests, Fourier transform infrared spectroscopy and liquid chromatography–mass spectrometry spectral studies. Based on the experimental results, the possible mechanisms were proposed. The reaction constants involved in the different steps of the mechanisms were evaluated. The catalytic constant (K_c) was also calculated for Ru(III) catalysis at different temperatures. The activation parameters with respect to the catalyst and slow step of the mechanisms were computed, and thermodynamic quantities were determined. Kinetic studies suggest that the active species of DPC and Ru(III) are found to be [Cu(H₂IO₆)(H₂O)₂] and [Ru(H₂O)₅OH]²⁺, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Complexes based on ethylene- and propylene-bridged-pentadentate-Fe(III)-units allow interplay between magnetic centers and multistability investigated by Mössbauer spectroscopy

The propylene-based ⁵3,3-L?=?[N,N′-Bis(1-hydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] and ethylene-based pentadentate ligand ⁵2,2-L?=?[N,N′-Bis(1-hydroxy-2-benzylidene)-1,5-diamino-3-azapentane] has been prepared. Complexation with Fe(III) yields high-spin (S?=?5/2) complexes of [Fe^III(⁵2,2-L)Cl] and [Fe^III(⁵3,3-L)Cl]. Such precursors were combined with [M(CN) _x ] ^y? (M?=?W(IV), Mo(IV), Ru(II), Co(III)) and heptanuclear and nonanuclear clusters of [M{(CN-Fe^III(⁵2,2-L)} _x ]Cl _y and [M{(CN-Fe^III(⁵3,3-L)} _x ]Cl _y resulted. Such starshaped hepta- and nonanuclear compounds are high-spin systems at room temperature. On cooling to 20 K in all presented ethylene compounds the iron(III) centers switch to a second high-spin state as proven by Mössbauer spectra with a yield of about 30%, i.e., multiple electronic transitions. The propylene compounds, however, perform a high-spin to low-spin transition. Mössbauer spectra taken during green light irradiation indicate changes in the population of the different electronic states, i.e. concerted inorganic reaction.     

Chemical tuning of high-spin complexes based on 3- and 4-hydroxy-pentadentate-Fe (III) complex-units investigated by Mössbauer spectroscopy

The pentadentate ligands 3-OH-⁵L?=?[N,N′-Bis(1,3-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] and 4-OH-⁵L?=?[N,N′-Bis(1,4-dihydroxy-2-benzylidene)-1,7-diamino-4-azaheptane] has been prepared by a Schiff base condensation between 1,7-diamino-4-azaheptane and the dihydroxybenzaldehyde. Complexation with Fe(III) yields high-spin (S?=?5/2) complexes of [Fe^III(3-OH-⁵L)Cl] and [Fe^III(4-OH-⁵L)Cl]. These precursors were combined with [M(CN) _x ] ^y? (M?=?W(IV), Mo(IV), Ru(II), Co(III)) and heptanuclear and nonanuclear clusters of [M{(CN-Fe^III(3-OH-⁵L)} _x ]Cl _y and [M{(CN-Fe^III(4-OH-⁵L)} _x ]Cl _y resulted. Such starshaped hepta- and nonanuclear compounds are high-spin systems at room temperature. On cooling to 10 K some of the iron(III) centers switch to a second high-spin state as proven by Mössbauer spectra, i.e. multiple electronic transitions. Parts of the compounds perform a high-spin to high-spin transition.     

Gold(I)-assisted catalysis – a comprehensive view on the [3,3]-sigmatropic rearrangement of allyl acetate

ABSTRACT

The unified reaction valley approach (URVA) combined with the local mode, ring puckering and electron density analysis is applied to elucidate the mechanistic differences of the non-catalysed and the Au[I]-N-heterocyclic carbene (NHC)-catalysed [3,3]-sigmatropic rearrangement of allyl acetate. Using a dual-level approach (DFT and DLPNO-CCSD(T)), the influence of solvation, counter-ions, bulky and electron withdrawing/donating substituents as well as the exchange of the Au[I]-NHC with a Au[I]-phosphine catalyst is investigated. The catalyst breaks up the rearrangement into two steps by switching between Au[I]–π and Au[I]–σ complexation, thus avoiding the energy-consuming CO cleavage in the first step. Based on local stretching force constants k^a(C=C), we derive for the first time a quantitative measure of the π-acidity of the Au[I] catalyst; in all catalysed reactions, the bond order n(C=C) drops from 2 to 1.65. The ring puckering analysis clarifies that all reactions start and end via a six-membered ring with a boat form. All Au[I]–σ-complex intermediates show a considerable admixture of the chair form. The non-catalysed [3,3]-sigmatropic rearrangement goes through a maximum of charge separation between the allyl and acetate units at the transition state, while all catalysed reactions proceed via a minimum of charge separation reached in the region of the Au[I]–σ-complex.     

Thermal transitions and degradative processes in Fe(III)-tetracarboxyphthalocyanine-grafted poly(N-vinylcarbazole)

The introduction of 2,9,16,23-tetracarboxy-Fe(III)phthalocyanine [Fe(III)tcPc] units onto fractions of poly(N-vinylcarbazole) (PVK) by Friedel-Crafts reaction leads to amorphous PVK-based grafted compounds that show major interchain distances by the wide-angle x-ray scattering (WAXS) technique. Glass transition temperatures of the products are lower than the main glass transition temperature of PVK and are attributed to local movements of the voluminous added groups. Dynamic thermogravimetric experiments show decarboxylation processes within the 250°C-500°C range and little weight loss. The large remaining residue, up to 70% of the sample at 800°C, is suggested to be the consequence of successive cross-linking reactions. The Fourier transform infrared (FTIR) spectrum of the residue is similar to that of the grafted sample before degradation.     

Studies on the adsorption of arsenic on calix[6]arene

p‐tert‐butyl calix[6]arene (PTC6) was synthesized and characterized by solid‐ and liquid‐state NMR and LC‐MS techniques. The adsorption of arsenite and arsenate on calix[6]arene under different pH conditions and adsorbate doses was studied. The maximum adsorption of arsenic species on calix[6]arene was observed around neutral pH and the adsorption density of As (III) was higher than that of As (V). The adsorption of neutral H₃AsO₃ and negatively charged H₂AsO molecules on calix[6]arene was attributed to the condensation reaction between hydroxyl groups of PTC6 and arsenic species. The complexation of arsenite with phenolic oxygen was confirmed by solid‐state ¹³C NMR CP‐MAS. Exo attack mechanism was proposed to describe the interaction of arsenous and arsenic acid molecules with PTC6. The specific interaction between calix[6]arene and arsenic species was further substantiated by zeta‐potential (ζ‐potential) measurements and free energy of adsorption. The free energy of adsorption ( ) estimated from Stern–Grahame equation was found to be 25 kJ/mole for As (III) and 19 kJ/mole for As (V). Copyright © 2010 John Wiley & Sons, Ltd.     

Photosensitized luminescence of thermostable polynuclear Eu(III) complexes

Tetranuclear europium(III) complexes, [Eu₄(μ-O)(L₁)₁₀] (L₁=2-hydroxy-4-octyloxybenzophenone,1) and [Eu₄(μ-O)(L₂)₁₀] (L₂=2-hydroxy-4-dodecyloxybenzophenone,2) were synthesized by the reaction of lanthanide nitrates with L₁ or L₂ in the presence of triethylamine in methanol. The photosensitized emission bands of the both Eu(III) complexes in THF-d₈ were observed around 579, 590, 615, 653, and 699 nm by the excitation of the ligands at 380 nm, whereas the emission from the mononuclear complex 3 containing ethanol molecules was almost quenched. The emission efficiencies were determined to be 3.1±0.1% for 1 and 3.9±0.1% for 2, respectively. The differential scanning calorimetry (DSC) measurements demonstrated that the decomposition points of 1 and 2 were 309 °C and 320 °C, respectively, indicating high thermostability of these complexes compared to the mononuclear Eu(III) complex 3 (250 °C). New strategy for designing stable rare earth compounds giving strong emission would be emphasized by introducing polynuclear complexes. Polynuclear complexes should open a wide range of molecular design for photosensitized luminescence and thermal stability.     

Selective surface chemistry of allyl alcohol and allyl aldehyde on Si(1 0 0)2×1: Competition of [2 + 2] CC cycloaddition with O-H dissociation and with [2 + 2] CO cycloaddition in bifunctional molecules

Competition between the CC functional group with the OH group in allyl alcohol and with the CO group in allyl aldehyde in the adsorption and thermal chemistry on Si(1 0 0)2×1 has been studied by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The similarities found in the C 1s and O 1s spectra for both molecules indicate that the O-H dissociation product for allyl alcohol and [2 + 2] CO cycloaddition product for allyl aldehyde are preferred over the corresponding [2 + 2] CC cycloaddition products. Temperature-dependent XPS and TPD studies further show that thermal evolution of these molecules gives rise to the formation of ethylene, acetylene, and propene on Si(1 0 0)2×1, with additional CO evolution only from allyl alcohol. The formation of these desorption products also supports that the [2 + 2] CC cycloaddition reaction does not occur. In addition, the formation of SiC at 1090 K is observed for both allyl alcohol and allyl aldehyde. We propose plausible surface-mediated reaction pathways for the formation of these thermal evolution products. The present work illustrates the crucial role of the Si(1 0 0)2×1 surface in selective reactions of the Si dimers with the O−H group in allyl alcohol and with the CO group in allyl aldehyde over the CC functional group common to both molecules.     

Gas‐phase basicities of acetophenones toward lanthanum cation [La(OMe)]

The relative free energy changes (lanthanum cation basicity, LaCB[L₂]) for the reaction [La(OMe)₂]L ? La(OMe) + 2L were determined in the gas phase for m‐ and p‐substituted acetophenones based on the measurement of ligand exchange equilibria using an FT‐ICR mass spectrometer. The substituent effect on ΔLaCB[L₂] of acetophenone is described in terms of the Yukawa–Tsuno equation, ΔG = ρ(σ° + r⁺ Δ σ ), with a ρ value of ?11.2 and an r⁺ value of 0.49. From this result, a ρ value of ?7.0 and an r⁺ value of 0.49 were estimated for the monomeric complex [LLa(OMe)] with the aid of theoretical calculations. This ρ value was found to be significantly smaller than that for protonation, and even smaller than Li⁺ basicity. Such a small ρ value has been attributed to the largely ionic (ion–dipole interaction) nature of the bonding interaction between La(OMe) and the carbonyl oxygen atom and, in part, to the long distance between La(OMe) and the substituent. Contrary to the ρ value, the r⁺ value is identical in both La(OMe) and Li⁺ basicities, suggesting that the r⁺ value of 0.49 can be regarded as a limiting one in a series of Lewis cation basicities of the acetophenone system, H⁺ (0.86) > Me₃Si⁺ (0.75) > Me₃Ge⁺ (0.71) > Cu⁺ (0.60) > Li⁺ = La(OMe) (0.49). Since the binding interaction between La(OMe) or Li⁺ and a neutral ligand is mostly electrostatic, the moderate r⁺ was interpreted to result from the redistribution of the induced positive charge within the acetophenone moiety upon binding with a metal ion rather than transfer of positive charge from a metal ion to the aromatic moiety. Copyright © 2010 John Wiley & Sons, Ltd.     

Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Desorptions- und Reaktionskinetik der Erdalkalien Calcium und Strontium mit Chlor an Wolfram. Part II: Kinetics of the Elementary Steps of the Surface Reaction M + Cl ⇌ MCl (M = Ca,Sr)

Desorption- and Reactionkinetics of the Alkaline Earth Elements Calcium and Strontium with Chlorine on a Tungsten Surface — Part II: Kinetics of the Elementary Steps of the Surface Reaction M + Cl ? MCl (M = Ca, Sr) Utilizing pulsed molecular-beam-technique the kinetics of desorption of Strontium, Calcium, and Chlorine as well as that of the molecules SrCl and CaCl, which are formed at the hot tungsten surface, was investigated. Thereby, the following values were obtained for the activation energies of desorption: ? = (3.76 ± 0.05) eV, ? = (3.32 ± 0.07) eV, ? = (4.16 ± 0.05) eV, ? = (4.2 ± 0.3) eV and ? = (3.9 ± 0.3) eV. Combining these results with the steady-state-results from part I [1] the temperature dependency of the rate constants of dissociation and recombination of MCl-molecules at the tungsten surface could be determined. The values obtained for the dissociation energies D of SrCl and CaCl on tungsten are (0.5 ± 0.5) eV and (0.3 ± 0.5) eV, respectively. The molecules are stabilized on the surface by the activation barrier for dissociation D? only, which was found to be (2.8 ± 0.5) eV for SrCl and (2.3 ± 0.5) eV for CaCl.     

‘Self‐terminating radical cyclizations’ – new insight into the mechanism of the termination step from computational studies

Computational methods were used to gain detailed insight into the mechanism of self‐terminating radical cyclizations, which are initiated by intermolecular addition of O‐centred radicals XO^? to alkynes. The calculations were performed for the reaction of NO, SO, and AcO^? with cyclodecyne ( 1 ) and 5‐cyclodecynone ( 2 ), respectively. Whereas radical addition and the subsequent transannular radical translocation steps are energetically highly favourable processes for the various XO^?, the terminating homolytic β‐fragmentation of the O? X bond in the intermediate α‐oxy radicals 10 – 13 shows a strong dependence on the nature of X. Using simplified model systems, the fragmentation was explored in detail, which revealed that the rate of this step is primarily determined by the strength of the O? X bond and only to a minor extent by the ability of the X moiety to stabilize an unpaired electron in the transition state. However, the cleavage is exothermic, when the released radical X^? is resonance stabilized, e.g. NO, SO, and Bn^?, respectively. In those cases where the unimolecular β‐fragmentation of the O? X bond is slow, termination could also proceed through a bimolecular radical chain process involving the α‐oxy radical intermediate 10 – 13 and the precursor of XO^?, e.g. the Barton PTOC ester 18 or Kim's dithiocarbamate 20 , respectively. Alternative termination mechanisms via oxidation of 10 – 13 can be ruled out under the usual experimental conditions of self‐terminating radical cyclizations. Copyright © 2010 John Wiley & Sons, Ltd.     

Transition from SU(2)L × SU(2)R × U(1)B-L representation to SU(2)L × U(1)Y by q-deformation and the corresponding classical breaking term of chiral U(2)

The minimal Standard Model exhibits a nontrivial chiral U(2) symmetry if the VEV and the hypercharge splitting Δ = (y-y)/2 of right-handed leptons (quarks) in a family vanish and Q = T₀ + Y independently in each helicity sector. As a generalization, we start with SU(2)_L × SU(2)_R × U(1)_(B-L) and introduce Δ as a continuous parameter which is a measure of explicit symmetry breakdown. Values 0 ? Δ ? 1/2 take the neutral generator of the isospin ½ representation to the singlet representation, i.e. ‘deformes’ the LR representation into the minimal Standard one. The corresponding classical O(3)-breaking term is a magnetic field perpendicular to the x₃-axis. A simple mapping on the fundamental Drinfeld-Jimbo q-deformed SU(2) representation is given.     

Oxidation of substituted triazines by sulfate radical anion (SO) in aqueous medium: a laser flash photolysis and steady state radiolysis study

Laser flash photolysis has been used to determine the bimolecular rate constants and the spectral nature of the intermediates obtained by the reaction of sulfate radical anion (SO) with 1,3,5‐triazine (T), 2,4,6‐trimethoxy‐1,3,5‐triazine (TMT), 2,4‐dioxohexahydro‐1,3,5‐triazine (DHT), and 6‐chloro N‐ethyl N'‐(1‐methylethyl)‐1,3,5‐triazine‐2,4‐diamine (atrazine, AT). The rate constants determined were in the range 4.6 × 10⁷–3 × 10⁹ dm³ mol^?1 s^?1 at pH 6. The transient absorption spectra obtained from the reaction of SO with T, TMT, DHT and AT has an absorption maximum in the region 320–350 nm and was found to undergo second‐order decay. The intermediate species is assigned to N‐yl C(OH) radical of T (TOH^?), carbon centered neutral radical of TMT, an OH‐adduct of AT and an N‐centered radical in the case of DHT. The interpretations on the experimental results obtained from TMT are supported by DFT calculation using Gaussian 03. Steady state radiolysis technique has also been used to investigate the degradation of AT induced by SO. The degradation profile indicated that about 99% of AT has been decomposed after an absorbed gamma‐radiation dose of 7.5 kGy. The degradation yield of AT (expressed as G(‐AT)) was found to be 0.26 µ mol J^?1. The degradation reactions initiated by SO may thus be employed as a potential alternative for ^?OH‐induced degradation of triazines. Copyright © 2007 John Wiley & Sons, Ltd.     

Simultaneous observation of low temperature 4f-4f and 3d-3d emission spectra in a series of Cr(III)(ox)Ln(III) assembly

We report here the low temperature emission spectra in the heterometal dinuclear 3d-4f assembled molecular system [(acac)₂Cr^III(μ-ox)Ln^III(HBpz₃)₂] (Cr(ox)Ln:acac⁻=acetylacetonate, ox²⁻=oxalate, HBpz₃⁻=hydrotris(pyrazol-1-yl)borate; Ln=La, Nd, Ho, Er , Tm and Yb) in comparison with those of Na[Cr(acac)₂(ox)] and [(HBpz₃)₂Ln(μ-ox)Ln(HBpz₃)₂](Ln=Nd and Er). From 10 to 150 K the Cr(ox)Ln complexes show a broad emission band around 800 nm from the ²E state of Cr(III) moiety. At room temperature no ²E-⁴A₂ emission was observed in the Cr(ox)Ln except for the La and Lu complexes. On warming from 10 to 300 K rapid quenching of the ²E-⁴A₂ emission of Cr(III) is suggested to result from the energy transfer from Cr to Ln in the Cr(ox)Ln. The excitation spectra and the life-time were also measured with monitoring the 4f-4f emission peaks of the Cr(ox)Yb complex.     

Enhanced fluorescence of Tb(III), Dy(III) perchlorate by salicylic acid in bis(benzoylmethyl) sulfoxide complexes and luminescence mechanism

Two novel ternary rare earth perchlorate complexes had been synthesized by using bis(benzoylmethyl) sulfoxide as first ligand (L=C₆H₅COCH₂SOCH₂COC₆H₅), salicylic acid as second ligand (L^′=C₆H₄OHCOO⁻). The compounds were characterized by elemental analysis, TG-DSC and molar conductivities in DMF solution. The composition was suggested as [REL₅L′](ClO₄)₂·nH₂O (RE=Tb, Dy; n=6, 8 ). Based on IR, ¹HNMR and UV spectra, it showed that the first ligand, bis(benzoylmethyl) sulfoxide (L), bonded with Tb(III), Dy(III) ions by the oxygen atom of sulfinyl group. The second ligand, salicylic acid group (L′), not only bonded with RE(III) ions by one oxygen atom of carboxyl group but also bonded with RE(III) ions by oxygen atom of phenolic hydroxyl group. In bis(benzoylmethyl) sulfoxide system, fluorescent spectra of the complexes showed that the luminescence of Tb(III), Dy(III) ions was enhanced by the second ligand salicylic acid. The ternary complexes had stronger fluorescence than the binary ones where only bis(benzoylmethyl) sulfoxide acted as ligand. Phosphorescent spectra of the two ligands indicated that the coordination of salicylic acid resulted in the matching extent increasing between the triplet state of ligand and excited state of the rare earths. The relationship between fluorescence lifetime and fluorescence intensity was also discussed.     

Synthesis, Characterization, Antioxidant Activity and DNA-Binding Studies of Three Rare Earth (III) Complexes with 1-(4-Aminoantipyrine)-3-tosylurea Ligand

1-(4-Aminoantipyrine)-3-tosylurea (H₂L) and its three lanthanide (III) complexes, M(H₂L)₃ 3NO₃ [where M = Nd(III), Sm(III) and Eu(III)], have been synthesized and characterized. In addition, the DNA-binding properties of the three complexes have been investigated by UV–vis (ultraviolet and visible) absorption spectroscopy, fluorescence spectroscopy, circular dichroism (CD) spectroscopy, cyclic voltammetry, and viscosity measurements. Results suggest that the three complexes bind to DNA via a groove binding mode. Furthermore, the antioxidant activity (superoxide and hydroxyl radical) of the metal complexes was determined by using spectrophotometer methods in vitro. These complexes were found to possess potent antioxidant activity and be better than standard antioxidants like vitamin C and mannitol. Absorption spectra of the complex 3 inTris-HCl buffer upon addition of calf-thymus DNA. [complex]=1×10^-5 M, [DNA]=(0-1) ×10^-5 M. Arrow shows the absorbance changing upon increasing DNA concentrations. Inset: plots of [DNA]/(ε_a – ε_f) versus [DNA] for the titration of DNA with the complex.     

Desorptions- und Reaktionskinetik der Erdalkalien Calcium und Strontium mit Chlor an Wolfram. Teil I: Chemisches Gleichgewicht der Oberflächenreaktion M + Cl = MCl im stationären Zustand (M = Ca,Sr)

Desorption- and Reactionkinetics of the Alkaline Earth Elements Calcium and Strontium with Chlorine on a Tungsten Surface — Part I: Chemical Equilibrium of the Surface Reaction M + Cl ? MCl in the Steady State (M = Ca, Br) Utilizing positive and negative surface ionization the reaction M + Cl = MCl (M = Ca, Sr) was studied at a hot tungsten surface under steady state conditions. Comparing the results obtained either by simultaneous M- and Cl₂ -exposures or by MCl₂ -exposure the existence of chemical equilibrium could be confirmed for the reaction in the temperature interval 1600 K.2000 K; at higher temperatures this equilibrium can be disturbed considerably by the desorption of the reacting components. From the experimental results we obtained under conditions of chemical equilibrium the energy of dissociation of MCl-molecules in the gasphase (D = (3.9 ± 0.15) eV, D = (4.2 ± 0.15)eV) and in the case of a strong disturbance of the equilibrium the difference between the activation energies of desorption and of dissociation of MCl-molecules on the surface (? - D? = (1.6 ± 0.2) eV, ? - D? = (1.4 ± 0.2) eV).