Kinetics and mechanism of one dipicolinato ligand substitution in the chromium(III)–bis(dipicolinato) complex: an unusual rate dependence on acid concentration

The Na[Cr(PDA)₂] · 2H₂O complex (PDA¹ = dipicolinic acid anion) and its aquation product, [Cr(PDA)(H₂O)₃]⁺, were prepared and characterized. The electronic spectra demonstrate that the bis(dipicolinato) complex undergoes very fast partial dechelation during dissolution. In acidic media, pH controlled, rapid protolytic and ring opening processes lead to coexistence of complexes with one tridentate (PDA) and the other bi- or mono-dentate (PDA). The kinetics of PDA ligand liberation were followed spectrophotometrically within the 0.1–2.0 M HClO₄ range at I = 2.0 M. The observed first-order rate constant depends on [H⁺] according to the equation: k _obs = A[H⁺]/(1 + B[H⁺] + C[H⁺]²). A reaction course via the uncharged [Cr(PDA)(HPDA)(H₂O)₂]⁰ complex is proposed. The observed rate increase, followed by rate retardation with [H⁺] increase, is attributed to the unreactive [Cr(PDA)(H₂PDA)(H₂O)₂]⁺ complex. In terms of the proposed mechanism, A, B, C parameters have been defined as: A = k ₁ Q ₁, B = Q ₁, C = Q ₁ Q ₂ where k ₁ is the rate constant of the Cr^III-carboxylato oxygen bond-breaking in the monodentate HPDA ligand, Q ₁ is a composite value describing protolytic and dechelation processes and Q ₂ is the protonation constant of the uncharged [Cr(PDA)(HPDA)(H₂O)₂]⁰ complex.     

Regulation of plastic from a circular economy perspective

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Dynamic Light Scattering and NMR Studies of Napin

We analyze the structure of napin (BngNAP1), a storage protein (m.w. 14.5 kDa) from Brassica napus. On the basis of the results of ¹H NMR spectroscopy and dynamic light scattering (DLS) studies, the overall shape and secondary structure of the molecule are estimated.     

First row divalent transition metal complexes of aryl-appended tris((pyridyl)methyl)amine ligands: syntheses, structures, electrochemistry, and hydroxamate binding properties

Divalent manganese, cobalt, nickel, and zinc complexes of 6-Ph(2)TPA (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-Ph(2)TPA)Mn(CH(3)OH)(3)](ClO(4))(2) (1), [(6-Ph(2)TPA)Co(CH(3)CN)](ClO(4))(2) (2), [(6-Ph(2)TPA)Ni(CH(3)CN)(CH(3)OH)](ClO(4))(2) (3), [(6-Ph(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (4)) and 6-(Me(2)Ph)(2)TPA (N,N-bis((6-(3,5-dimethyl)phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-(Me(2)Ph)(2)TPA)Ni(CH(3)CN)(2)](ClO(4))(2) (5) and [(6-(Me(2)Ph)(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (6)) have been prepared and characterized. X-ray crystallographic characterization of 1A.CH(3)()OH and 1B.2CH(3)()OH (differing solvates of 1), 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN revealed mononuclear cations with one to three coordinated solvent molecules. In 1A.CH(3)()OH and 1B.2CH(3)()OH, one phenyl-substituted pyridyl arm is not coordinated and forms a secondary hydrogen-bonding interaction with a manganese bound methanol molecule. In 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN, all pyridyl donors of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands are coordinated to the divalent metal center. In the cobalt, nickel, and zinc derivatives, CH/pi interactions are found between a bound acetonitrile molecule and the aryl appendages of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands. (1)H NMR spectra of 4 and 6 in CD(3)NO(2) solution indicate the presence of CH/pi interactions, as an upfield-shifted methyl resonance for a bound acetonitrile molecule is present. Examination of the cyclic voltammetry of 1-3 and 5 revealed no oxidative (M(II)/M(III)) couples. Admixture of equimolar amounts of 6-Ph(2)TPA, M(ClO(4))(2).6H(2)O, and Me(4)NOH.5H(2)O, followed by the addition of an equimolar amount of acetohydroxamic acid, yielded the acetohydroxamate complexes [((6-Ph(2)TPA)Mn)(2)(micro-ONHC(O)CH(3))(2)](ClO(4))(2) (8), [(6-Ph(2)TPA)Co(ONHC(O)CH(3))](ClO(4))(2) (9), [(6-Ph(2)TPA)Ni(ONHC(O)CH(3))](ClO(4))(2) (10), and [(6-Ph(2)TPA)Zn(ONHC(O)CH(3))](ClO(4))(2) (11), all of which were characterized by X-ray crystallography. The Mn(II) complex 8.0.75CH(3)()CN.0.75Et(2)()O exhibits a dinuclear structure with bridging hydroxamate ligands, whereas the Co(II), Ni(II), and Zn(II) derivatives all exhibit mononuclear six-coordinate structures with a chelating hydroxamate ligand.     

Atmospheric chemistry of CF3OCF2CF2H and CF3OC(CF3)2H: reaction with Cl atoms and OH radicals, degradation mechanism, global warming potentials, and empirical relationship between k(OH) and k(Cl) for organic compounds

Using FTIR smog chamber techniques, k(Cl + CF3OCF2CF2H) = (2.70 +/- 0.52) x 10(-16), k(OH + CF3OCF2CF2H) = (2.26 +/- 0.18) x 10(-15), k(Cl + CF3OC(CF3)2H) = (1.58 +/- 0.27) x 10(-18) and k(OH + CF3OC(CF3)2H) = (3.26 +/- 0.95) x 10(-16) cm3 molecule(-1) s(-1) were measured. The atmospheric lifetimes of CF3OCF2CF2H and CF3OC(CF3)2H are estimated to be 27 and 216 years, respectively. Chlorine atom initiated oxidation of CF3OCF2CF2H in 700 Torr of air in the presence of NO(x) gives CF3OC(O)F in a molar yield of 36 +/- 5% and COF2 in a molar yield of 174 +/- 9%, whereas oxidation of CF3OC(CF3)2H gives CF3OC(O)CF3 and COF2 in molar yields that are indistinguishable from 100%. Quantitative infrared spectra were recorded and used to estimate global warming potentials of 3690 and 8230 (100 year time horizon, relative to CO2) for CF3OCF2CF2H and CF3OC(CF3)2H, respectively. All experiments were performed in 700 Torr of N2/O2 diluent at 296 +/- 2 K. An empirical relationship can be used to estimate the preexponential factor, which can be combined with k(298 K) to give the temperature dependence of reactions of OH radicals with organic compounds proceeding via H-atom abstraction: log(A/n) = (0.239 +/- 0.027) log(k(OH)/n) - (8.69 +/- 0.372), k(OH) is the rate constant at 298 K and n is the number of H atoms. The rates of H-atom abstraction by OH radicals and Cl atoms at 298 K from organic compounds are related by the expression log(k(OH)) = (0.412 +/- 0.049) log(k(Cl)) - (8.16 +/- 0.72). The utility of these expressions and the atmospheric chemistry of the title hydrofluoroethers are discussed.     

Synchrotron radiation circular dichroism spectroscopy of ribose and deoxyribose sugars, adenosine, AMP and dAMP nucleotides.

Synchrotron radiation circular dichroism (SRCD) spectra of ribose and deoxyribose sugars, adenosine, AMP and dAMP nucleotides and cyclic derivatives were measured in the vacuum ultraviolet region (down to 168 nm for sugars and 175 nm for adenine derivatives) and at different pH values (3, 6-7, 9-10) and temperatures (between 5 and 45 degrees C). The information content in the VUV region is important since the CD bands strongly depend on the chemical structure of the sugar, the presence and orientation of a phosphate group and the protonation state of adenine. On the other hand, single or double deprotonation of the phosphoric acid group has no influence on the spectra. We assign the vacuum ultraviolet (VUV) CD bands of the nucleoside and nucleotides to be due mainly to n-->pi* transitions in the adenine nucleobase based on a comparison with the absorption spectra. The CD bands of the sugars are due to n(O -->sigma*) transitions and are much smaller than the CD signal from the nucleotides in the VUV region. Bands are assigned to both pyranose and open-chain forms.     

Elimination of SAS Interferences in Catalytic Adsorptive Stripping Voltammetric Determination of Cr(VI) by Means of Fumed Silica

In the work the procedure of chromium(VI) determination by catalytic adsorptive stripping voltammetry (CAdSV) with application of fumed silica, is presented. Two variants of the method are proposed: in the first fumed silica is put directly to the electrolytic cell containing tested solution, in the second the silica is shaken with the sample and next centrifuged. The effectiveness of many surface‐active substances removal from synthetic solutions as well as natural water samples, is studied. In the experiments the fumed silica (Sigma‐Aldrich) of the specific surface area in the range 200–390 m² g^?1 was used. Two types of the working electrodes were applied, i.e., hanging mercury drop electrode (HMDE) and cyclic renewable mercury film electrode (Hg(Ag)FE). In the silica presence i) the relative standard deviation (RSD) for 0.1 μg L^?1 Cr(VI) is <2% (HMDE) and <5% (Hg(Ag)FE), n=7, ii) the detection limits estimated deposition time 20 s were respectively 14 ng L^?1 (HMDE) and 22 ng L^?1 (Hg(Ag)FE). The accuracy of the method was tested by studying the recovery of Cr(VI) from spiked natural water samples.     

Electrochemical study of 18-crown-6-Tl+ complexes in binary solvent mixtures

Summary The formation constants,K _S, of the 18-crown-6 complex with thallium(I) ion were studied by polarographic measurements in binary mixtures of acetonitrile, acetone, tetrahydrofuran, and dimethylsulfoxide with water, as a function of the solvent mole fraction. In all the cases, the variation of the stability constant can be described by the empirical relation logK _S=a[(–1)/(2+1)]+b where stands for relative permittivity of a given mixture anda andb mark the regression coefficients. The values ofa calculated for four series of binary mixtures showed correlation with the Gutmann donor numbers of the neat organic solvents which form the mixture.On leave from the Department of Chemistry, Jingzhou Teacher's College, Jingzhou, Hubei, China     

Synthesis,characterization and biological activity of some 1,2,4‐triazine derivatives

4‐Amino‐6‐methyl‐3‐(2H)‐thioxo‐5‐(4H)‐oxo‐1,2,4‐triazine ( 1 ) was condensed with 2‐methyl (or phenyl)‐4H‐3,1‐benzoxazin‐4‐one ( 5a,b ) in boiling acetic acid to give compounds 8‐11 . Reacting 1 with chloroacetyl chloride afforded the corresponding chloroacetamido and triazinothiadiazine derivatives 12 and 13 . Condensing 2 with succinic anhydride and/or phthalic anhydride yielded compounds 14 and 15 . Benzoylation of 4‐amino‐6‐methyl‐3‐(2H)‐thioxo‐5‐(4H)‐oxo‐2‐(2,3,4,5‐tetra‐O‐acetyl‐α‐D‐glucopyra‐nosyl)‐1,2,4‐triazine ( 19 ) afforded the corresponding 4‐N,N‐dibenzoyl derivative 20 . Deblocking of the N‐2 glycoside 21 and the S‐glycoside 22 by methanolic ammonia gave compounds 23 and 24 . Acetylation of 4‐amino glycoside 25a afforded the corresponding 4‐mono‐ and 4‐diacetyl derivatives 26 and 27 . Deamination of 25a,b yielded compounds 28a,b . Methylation of compound 28b afforded the corresponding N4‐ and S‐methyl derivatives 29 and 30 .