Photochemistry of peroxoborates: borate inhibition of the photodecomposition of hydrogen peroxide

The UV absorbance and photochemical decomposition kinetics of hydrogen peroxide in borate/boric acid buffers were investigated as a function of pH, total peroxide concentration, and total boron concentration. At higher pH borate/boric acid inhibits the photodecomposition of hydrogen peroxide (molar absorptivity and quantum yield of H(2)O(2) and HO(2) (-), (19.0+/-0.3) M(-1) cm(-1) and 1, and (237+/-7) M(-1) cm(-1) and 0.8+/-0.1, respectively). The results are consistent with the equilibrium formation of the anions monoperoxoborate, K(BOOH)=[H(+)][HOOB(OH)(3) (-)]/([B(OH)(3)][H(2)O(2)]), 2.0 x 10(-8), R. Pizer, C. Tihal, Inorg. Chem. 1987, 26, 3639-3642, and monoperoxodiborate, K(BOOB)=[BOOB(2-)]/([B(OH)(4) (-)][HOOB(OH)(3) (-)]), 1.0+/-0.3 or 4.3+/-0.9, depending upon the conditions, with molar absorptivity, (19+/-1) M(-1) cm(-1) and (86+/-15) M(-1) cm(-1), respectively, and respective quantum yields, 1.1+/-0.1 and 0.04+/-0.04. The low quantum yield of monoperoxodiborate is discussed in terms of the slower diffusion apart of incipient (.)OB(OH)(3) (-) radicals than may be possible for (.)OH radicals, or a possible oxygen-bridged cyclic structure of the monoperoxodiborate.     

2-芳基吲哚的敏化光氧化偶合反应

本文研究了十七种2-芳基吲哚(1a-1q)在甲醇-乙酸介质中的亚甲基蓝(MB)敏化光氧化反应, 发现有十五种吲哚(1a-1o)以85%-95%的产率给出2,2'-二芳基-[2,3'-联-1H-吲哚]-3(2H)-酮(2a-2o), 而2-(4-硝基苯基]吲哚(1p)和2-联苯基吲哚(1q)则分别生成2-甲氧基-2-(4-硝基苯基)-1,2-二氢-3H-吲哚-3-酮(7p)和2-联苯基-4H-3,1-苯并恶嗪-4-酮(11q), 其中7p在分离过程中失去甲醇分子给出2-(4-硝基苯基)-3H-吲哚-3-酮(10p)。     

Synthesis of Derivatives of Chlorin P6 Trimethyl Ester

The Vilsmeier reaction of nickel(II) chlorin P₆ trimethyl ester with 3-dimethyl-aminoacrolein yielded nickel(II) chlorin P₆ 20-(2-formylvinyl) trimethyl ester and nickel(II) chlorin P₆ 3-(1-hydroxyethyl)-3-devinyl-20-(2-formylvinyl) trimethyl ester. Also, the outgrowths of nickel(II) chlorin P₆ 20-(2-formyl) trimethyl ester and nickel(II) chlorin P₆ 3-(2-formylvinyl)-3-devinyl-20-(2-formyl) trimethyl ester were obtained by Vilsmeier reaction with dimethylformamide. By treating the derivatives of nickel(II) 20-(2-formyl)-chlorin and nickel(II) 3-(2-formylvinyl)-20-(2-formyl)-chlorin with trifluoracetic acid, the removal of the central nickel(II) ion was accomplished. The derivatives of 20-(2-formyl)-chlorin and 3-(2-formylvinyl)-20-(2-formyl)-chlorin demonstrated considerable bathochromic shift of the major absorption band in the red region of the optical spectrum.     

Synthesis of derivatives of 1-phenylhydropyrimidines

The synthesis has been effected, via the corresponding N-phenyl-ß-aminopropionic acids, of 1-(o-methoxyphenyl)-, 1-(o-ethoxyphenyl)-, and 1-(o-tolyl)dihydrouracils and also of 1-(o-methoxyphenyl)-, 1-(o-ethoxyphenyl)-, and 1-(o-tolyl)-2-thiodihydrouracils. The dihydrouracits and thiodihydrouracils obtained have been reduced with LiAlH₄ to the corresponding 2-oxohexahydro-, and 2-thioxohexahydropyrimidines. By the action of bromine and the subsequent splitting out of HBr, the dihydrouracils have been converted into 1-(o-methoxyphenyl)-, 1-(o-ethoxyphenyl)-, and 1-(o-tolyl)uracils.     

Kinetics and mechanisms of S(IV) reductions of bromite and chlorite ions

The reaction of bromite with aqueous S(IV) is first order in both reactants and is general-acid catalyzed. The reaction half-lives vary from 5 ms (p[H+] 5.9) to 210 s (p[H+] 13.1) for 0.7 mM excess S(IV) at 25 degrees C. The proposed mechanism includes a rapid reaction (k(1) = 3.0 x 10(7) M(-1) s(-1)) between BrO(2)(-) and SO(3)(2-) to form a steady-state intermediate, (O(2)BrSO(3))(3-). General acids assist the removal of an oxide ion from (O(2)BrSO(3))(3-) to form OBrSO(3)(-), which hydrolyzes rapidly to give OBr(-) and SO(4)(2-). Subsequent fast reactions between HOBr/OBr(-) and SO(3)(2-) give Br(-) and SO(4)(2-) as final products. In contrast, the chlorite reactions with S(IV) are 5-6 orders of magnitude slower. These reactions are specific-acid, not general-acid, catalyzed. In the proposed mechanism, ClO(2)(-) and SO(3)H(-)/SO(2) react to form (OClOSO(3)H)(2)(-) and (OClOSO(2))(-) intermediates which decompose to form OCl(-) and SO(4)(2-). Subsequent fast reactions between HOCl/OCl(-) and S(IV) give Cl- and SO(4)(2-) as final products. SO(2) is 6 orders of magnitude more reactive than SO(3)H-, where k(5)(SO(2)/ClO(2)(-)) = 6.26 x 10(6) M(-1) s(-1) and k(6)(SO(3)H(-)/ClO(2)(-)) = 5.5 M(-1) s(-1). Direct reaction between ClO(2)(-) and SO(3)(2-) is not observed. The presence or absence of general-acid catalysis leads to the proposal of different connectivities for the initial reactive intermediates, where a Br-S bond forms with BrO(2)(-) and SO(3)(2-), while an O-S bond forms with ClO(2)(-) and SO(3)H-.     

Reactivity of TCNE or TCNQ derivatives of quinonoid zwitterions: platinum-induced HCN elimination vs oxidative-addition

The reaction of the functional, zwitterionic quinonoid molecule (6E)-4-(butylamino)-6-(butyliminio)-3-oxo-2-(1,1,2,2-tetracyanoethyl)cyclohexa-1,4-dien-1-olate, [C(6)H-2-{C(CN)(2)C(CN)(2)H}]-4,6-(···NH n-Bu)(2)-1,3(···O)(2) (2), which has been previously prepared by regioselective insertion of TCNE into the C-H bond adjacent to the C···O bonds of the zwitterionic benzoquinone monoimine (6E)-4-(butylamino)-6-(butyliminio)-3-oxocyclohexa-1,4-dien-1-olate, C(6)H(2)-4,6-(···NHn-Bu)(2)-1,3-(···O)(2) (1), with 2 equiv of [Pt(C(2)H(4))(PPh(3))(2)], afforded the Pt(0) complex [Pt(PPh(3))(2)(4)] (6) (4 = 2-HCN; (6E)-4-(butylamino)-6-(butyliminio)-3-oxo-2-(1,2,2-tricyanoethenyl)cyclohexa-1,4-dien-1-olate), in which a tricyanoethenyl moiety is π-bonded to the metal. A metal-induced HCN elimination reaction has thus taken place. The same complex was obtained directly by the reaction of 1 equiv of the Pt(0) complex [Pt(C(2)H(4))(PPh(3))(2)] with the olefinic ligand [C(6)H-2-{C(CN)═C(CN)(2)}]-4,6-(···NHn-Bu)(2)-1,3-(···O)(2)) (4), previously obtained by the reaction of 2 with NEt(3) in THF. A similar reactivity pattern was observed between 2 and 2 equiv of the Pd(0) precursor [Pd(dba)(2)] in the presence of dppe, which led to [Pd(dppe)(4)] (7), which was also directly obtained from 4 and 1 equiv [Pd(dba)(2)]/dppe. In contrast to the behavior of the TCNE derivative 2, the reaction of the TCNQ derivative (6E)-4-(butylamino)-6-(butyliminio)-2-(dicyano(4-(dicyanomethyl)phenyl)methyl)-3-oxocyclohexa-1,4-dien-1-olate, [C(6)H-2-{C(CN)(2)p-C(6)H(4)C(CN)(2)H}]-4,6-(···NHn-Bu)(2)-1,3-(···O)(2)) (3), with 2 equiv of [Pt(C(2)H(4))(PPh(3))(2)] led to formal oxidative-addition of the C-H bond of the C(CN)(2)H moiety to give the Pt(II) hydride complex trans-[PtH(PPh(3))(2){N═C═C(CN)p-C(6)H(4)C(CN)(2)-2-[C(6)H-4,6-(···NHn-Bu)(2)-1,3-(···O)(2))}] (8). The molecular structures of 3, 4, 6·0.5(H(2)O), and 8·3(CH(2)Cl(2)) have been determined by single-crystal X-ray diffraction.     

Synthesis of Tri-And Tetrasaccharides Present in the Linkage Region of Heparin and Heparan Sulphate

Abstract

The methyl glycosides of the the tri-and tetrasaccharides present in the linkage region of heparin, methyl O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside and methyl O-(β-D-glucopyranosyluronic acid)-(l→3)-O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside sodium salt, were synthesized together with their phosphate containing analogues, methyl O-(β-D-galactopyranosyl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside 2-(disodium phosphate) and methyl O-(β-D-glucopyranosyluronic acid)-(l→3)-O-(β-D-galactopyrano-syl)-(l→3)-O-(β-D-galactopyranosyl)-(l→4)-β-D-xylopyranoside 2-(disodium phosphate) sodium salt, which are glycosides of the structure found in the linkage region of heparan sulphate.     

哒嗪酮的乙酰胺类化合物的合成及生物活性

2-叔丁基-4-氯-5-羟基-哒嗪-3(2H)-酮(3)与相应的N-烷基或N,N-二烷基氯乙酰胺(4a-4l)反应,合成了2-叔丁基-5-[(N-烷基或N,N-二烷基乙酰胺)氧基]-4-氯-哒嗪-3(2H)-酮(1a-1l),生物活性测定结果表明部分化合物(1a-1l)具有杀虫活性。     

Chemiluminescence determination of fluoroquinolones using Fenton system in the presence of terbium(iii) ions

A simple new chemiluminescent, CL, method is described for the determination of fluoroquinolones such as: ciprofloxacin (CF), norfloxacin (NF), and ofloxacin (OF). This method is based on the measurement of terbium(iii) emission. This emission follows an energy transfer to the uncomplexed terbium(iii) ions from the excited products of fluoroquinolone oxidations. Under optimum conditions, calibration graphs were obtained for 2 × 10(-8)-2 × 10(-6) mol L(-1) of NF; 3 × 10(-8)-2 × 10(-6) mol L(-1) of CF and 4 × 10(-7)-5 × 10(-5) mol L(-1) of OF. The detection limits are 7 × 10(-9) mol L(-1) norfloxacin, 1 × 10(-8) mol L(-1) ciprofloxacin and 1.5 × 10(-7) mol L(-1) ofloxacin. The method was successfully applied to the determination of these drugs in pharmaceutical formulations.     

Synthesis of Urinary Metabolites of Retinoic Acid

Urinary metabolites 5-methyl-5-[2-(2,6,6-trimethyl -3-oxo-1-cyclohexen-1-yl)-vinyl]-2-tetrahydrofuranone (1) and 5-[2-(6-hydroxymethyl-2, 6-dimethyl-3-oxo-1- cyclohexen-1-yl)vinyl]-5-methyl-2-tetrahydrofuranone (2) of retinoic acid have been synthesized from 4-[2,2,6-trimethyl-3-(tetrahydro-2 H -pyran-2-yl)oxy-1-cyclohexen-1-yl]-3-buten-2-one (4) and methyl 2-(3,3-ethylenedioxy-1-butenyl)-1, 3-dimethyl-4-oxo-2-cyclohexene-1-carboxylate (5) .     

Magneto-optics of Ferritin

Measurements of Rayleigh light scattering, nonlinear light scattering in DC magnetic fields, and the Cotton-Mouton effect were carried out for 15 mM NaCl and water solutions of ferritin at room temperature. The spherical geometry of the molecule implies that it is optically isotropic. Such a macromolecule should not manifest magnetic anisotropy; however, in solution it shows induced magnetic birefringence (Cotton-Mouton effect) and changes in the intensity of the scattered light components. The analysis of the obtained results indicates the deformation of linear optical polarizability induced in the ferritin by a magnetic field as the main source of the magneto-optical phenomena observed. Light scattering and the CM effects theoretically depend on the linear magneto-optical polarizability, chi, and the nonlinear magneto-optical polarizability, eta. Using the theory describing the phenomena as well as the experimental data, the values of the anisotropy of linear magneto-optical polarizability components, chi(parallel) - chi(perpendicular) = -(1.3 +/- 0.7) x 10(-22) [cm3] (in SI units chi(parallel) - chi(perpendicular) = -(2.0 +/- 1.2) x 10(-33) [m3]), the linear optical polarizability, alpha = (alpha(parallel) + 2alpha(perpendicular))/3 = (3.9 +/- 1.0) x 10(-20) [cm3] (in SI units alpha = (3.52 +/- 0.09)x10(-4) [Cm2 V(-1)]), and its anisotropy, kappa(alpha) = (alpha(parallel) - alpha(perpendicular))/3alpha = -(0.06+/-0.03), nonlinear magneto-optical polarizability, eta = (eta(parallel) + 2eta(perpendicular))/3 = -(4.7 +/- 0.9) x 10(-30) [cm3 Oe(-2)] (in SI units eta = -(6.7 +/- 1.3) x 10(-18) [Cm4 V(-1) A(-2)]) and its anisotropy, kappa(eta) = (eta[parallel) - eta(perpendicular))/3eta = -(0.15 +/- 0.10), were deduced. Here alpha(parallel), eta(parallel), alpha(perpendicular), eta(perpendicular) are the optical and magneto-optical polarizability components along the parallel and the perpendicular axes of the axially symmetric molecule, respectively.     

Influence of terpyridine as pi-acceptor ligand on the kinetics and mechanism of the reaction of NO with ruthenium(III) complexes

The kinetics of the unusually fast reaction of cis- and trans-[Ru(terpy)(NH3)2Cl]2+ (with respect to NH3; terpy=2,2':6',2"-terpyridine) with NO was studied in acidic aqueous solution. The multistep reaction pathway observed for both isomers includes a rapid and reversible formation of an intermediate Ru(III)-NO complex in the first reaction step, for which the rate and activation parameters are in good agreement with an associative substitution behavior of the Ru(III) center (cis isomer, k1=618 +/- 2 M(-1) s(-1), DeltaH(++) = 38 +/- 3 kJ mol(-1), DeltaS(++) = -63 +/- 8 J K(-1) mol(-1), DeltaV(++) = -17.5 +/- 0.8 cm3 mol(-1); k -1 = 0.097 +/- 0.001 s(-1), DeltaH(++) = 27 +/- 8 kJ mol(-1), DeltaS(++) = -173 +/- 28 J K(-1) mol(-1), DeltaV(++) = -17.6 +/- 0.5 cm3 mol(-1); trans isomer, k1 = 1637 +/- 11 M(-1) s(-1), DeltaH(++) = 34 +/- 3 kJ mol(-1), DeltaS(++) = -69 +/-11 J K(-1) mol(-1), DeltaV(++) = -20 +/- 2 cm3 mol(-1); k(-1)=0.47 +/- 0.08 s(-1), DeltaH(++)=39 +/- 5 kJ mol(-1), DeltaS(++) = -121 +/-18 J K(-1) mol(-1), DeltaV(++) = -18.5 +/- 0.4 cm3 mol(-1) at 25 degrees C). The subsequent electron transfer step to form Ru(II)-NO+ occurs spontaneously for the trans isomer, followed by a slow nitrosyl to nitrite conversion, whereas for the cis isomer the reduction of the Ru(III) center is induced by the coordination of an additional NO molecule (cis isomer, k2=51.3 +/- 0.3 M(-1) s(-1), DeltaH(++) = 46 +/- 2 kJ mol(-1), DeltaS(++) = -69 +/- 5 J K(-1) mol(-1), DeltaV(++) = -22.6 +/- 0.2 cm3 mol(-1) at 45 degrees C). The final reaction step involves a slow aquation process for both isomers, which is interpreted in terms of a dissociative substitution mechanism (cis isomer, DeltaV(++) = +23.5 +/- 1.2 cm3 mol(-1); trans isomer, DeltaV(++) = +20.9 +/- 0.4 cm3 mol(-1) at 55 degrees C) that produces two different reaction products, viz. [Ru(terpy)(NH3)(H2O)NO]3+ (product of the cis isomer) and trans-[Ru(terpy)(NH3)2(H2O)]2+. The pi-acceptor properties of the tridentate N-donor chelate (terpy) predominantly control the overall reaction pattern.     

Synthesis and characterization of the novel monoamide derivatives of Gd-TTDA

For this study, the N'-monoamide derivatives of TTDA (3,6,10-tri(carboxymethyl)-3,6,10-triazadodecanedioic acid), N'-methylamide (TTDA-MA), N'-benzylamide (TTDA-BA), and N'-2-methoxybenzylamide (TTDA-MOBA), were synthesized. Their protonation constants and stability constants (log K(ML)'s) formed with Ca(2+), Zn(2+), Cu(2+), and Gd(3+) were determined by potentiometric titration in 0.10 M Me(4)NCl at 25.0 +/- 0.1 degrees C. The relaxivity values of [Gd(TTDA-MA)](-), [Gd(TTDA-BA)](-), and [Gd(TTDA-MOBA)](-) remained constant with respect to pH changes over the range 4.5-12.0. The (17)O NMR chemical shift of H(2)O induced by [Dy(TTDA-MA)(H(2)O)](-) at pH 6.80 showed 0.9 inner-sphere water molecules. Water proton relaxivity values for [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) at 37.0 +/- 0.1 degrees C and 20 MHz are 3.89, 4.21, and 4.25, respectively. The water-exchange lifetime (tau(M)) and rotational correlation time (tau(R)) of [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) are obtained from reduced the (17)O relaxation rate and chemical shifts of H(2)(17)O. The (2)H NMR longitudinal relaxation rates of the deuterated diamagnetic lanthanum complexes for the rotational correlation time were also thoroughly investigated. The water-exchange rates (K(298)(ex) for [Gd(TTDA-MA)(H(2)O)](-), [Gd(TTDA-BA)(H(2)O)](-), and [Gd(TTDA-MOBA)(H(2)O)](-) are lower than that of [Gd(TTDA)(H(2)O)](2)(-) but significantly higher than those of [Gd(DTPA)(H(2)O)](2)(-) and [Gd(DTPA-BMA)(H(2)O)]. The rotational correlation times for [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) are significantly longer than those of [Gd(TTDA)(H(2)O)](2)(-) and [Gd(DTPA)(H(2)O)](2)(-) complexes. The marked increase of the relaxivity of [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) results mainly from their longer rotational correlation time. The noncovalent interaction between human serum albumin (HSA) and [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) complexes containing a hydrophobic substituent was investigated by measuring the water proton relaxation rate of the aqueous solutions. The binding association constant (K(A)) values are 1.0 +/- 0.2 x 10(3) and 1.3 +/- 0.2 x 10(3) M(-1) for [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-), which indicates a stronger interaction of [Gd(TTDA-BA)(H(2)O)](-) and [Gd(TTDA-MOBA)(H(2)O)](-) with HSA.     

Kinetics of Dissociation of Iron(III) Complexes of Tiron in Aqueous Acid

The kinetics of dissociation of the mono, bis, and tris complexes of Tiron (1,2-dihydroxy-3,5-benzenedisulfonate) have been studied in acidic aqueous solutions in 1.0 M HClO(4)/NaClO(4), as a function of [H(+)] and temperature. In general, the kinetics can be explained by two reactions, (H(2)O)Fe(L)(n)(-1) + H(2)L right arrow over left arrow (H(2)O)Fe(L(n)H) + H(+) (k(n), k(-n)) and (HO)Fe(L)(n)(-1) + H(2)L right arrow over left arrow (H(2)O)Fe(L(n)H) (k(n)', k(-n)'), a rapid equilibrium, (H(2)O)Fe(L(n)H) right arrow over left arrow (H(2)O)Fe(L)(n) + H(+) (K(cn)), and the formation constant (H(2)O)Fe(L)(n)(-1) + H(2)L right arrow over left arrow (H(2)O)Fe(L)(n) + 2H(+). For n = 1, the reaction was observed at 670 nm, and at [H(+)] of 0.05-0.5 M at temperatures of 2.0, 14.0, 25.0, and 36.7 degrees C. For n = 2, the analogous conditions are 562 nm, at [H(+)] of 1.5 x 10(-3) to 1.4 x 10(-2) M at temperatures of 2.0, 9.0, and 14.0 degrees C. For n = 3, the conditions are 482 nm, at pH 4.5-5.7 in 0.02 M acetate buffer at temperatures of 1.8, 8.0, and 14.5 degrees C. The rate or equilibrium constants (25 degrees C) with DeltaH or DeltaH degrees (kcal mol(-1)) and DeltaS or DeltaS degrees (cal mol(-1) K(-1)) in brackets are as follows: for n = 1, k(1) = 2.3 M(-1) s(-1) (8.9, -27.1), k(-1) = 1.18 M(-1) s(-1) (4.04, -44.8), K(c1) = 0.96 M (-9.99, -33.6), K(f1) = 2.01 M (-5.14, -15.85); for n = 2, k(-2)/K(c2) = 1.9 x 10(7) (19.9, 41.5) and k(-2)'/K(c2) = 1.85 x 10(3) (1.4, -38.8) and a lower limit of K(c2) > 0.015 M; for n = 3, k(3) = 7.7 x 10(3) (15.8, 12.3), k(-3) = 1.7 x 10(7) (16.2, 28.9), K(c3) = 7.4 x 10(-5) M (4.1, -5.1), and K(f3) = 3.35 x 10(-8) (3.7, -21.7). From the variations in rate constants and activation parameters, it is suggested that the Fe(L)(2) and Fe(L)(3) complexes undergo substitution by dissociative activation, promoted by the catecholate ligands.     

Active Thermochemical Tables: accurate enthalpy of formation of hydroperoxyl radical, HO2

Through the use of the Active Thermochemical Tables approach, the best currently available enthalpy of formation of HO2 has been obtained as delta(f)H(o)298 (HO2) = 2.94 +/- 0.06 kcal mol(-1) (3.64 +/- 0.06 kcal mol(-1) at 0 K). The related enthalpy of formation of the positive ion, HO2+, within the stationary electron convention is delta(f)H(o)298 (HO2+) = 264.71 +/- 0.14 kcal mol(-1) (265.41 +/- 0.14 kcal mol(-1) at 0 K), while that for the negative ion, HO2- (within the same convention), is delta(f)H(o)298 (HO2-) = -21.86 +/- 0.11 kcal mol(-1) (-21.22 +/- 0.11 kcal mol(-1) at 0 K). The related proton affinity of molecular oxygen is PA298(O2) = 100.98 +/- 0.14 kcal mol(-1) (99.81 +/- 0.14 kcal mol(-1) at 0 K), while the gas-phase acidity of H2O2 is delta(acid)G(o)298 (H2O2) = 369.08 +/- 0.11 kcal mol(-1), with the corresponding enthalpy of deprotonation of H2O2 of delta(acid)H(o)298 (H2O2) = 376.27 +/- 0.11 kcal mol(-1) (375.02 +/- 0.11 kcal mol(-1) at 0 K). In addition, a further improved enthalpy of formation of OH is briefly outlined, delta(f)H(o)298 (OH) = 8.93 +/- 0.03 kcal mol(-1) (8.87 +/- 0.03 kcal mol(-1) at 0 K), together with new and more accurate enthalpies of formation of NO, delta(f)H(o)298 (NO) = 21.76 +/- 0.02 kcal mol(-1) (21.64 +/- 0.02 kcal mol(-1) at 0 K) and NO2, delta(f)H(o)298 (NO2) = 8.12 +/- 0.02 kcal mol(-1) (8.79 +/- 0.02 kcal mol(-1) at 0 K), as well as H(2)O(2) in the gas phase, delta(f)H(o)298 (H2O2) = -32.45 +/- 0.04 kcal mol(-1) (-31.01 +/- 0.04 kcal mol(-1) at 0 K). The new thermochemistry of HO2, together with other arguments given in the present work, suggests that the previous equilibrium constant for NO + HO2 --> OH + NO2 was underestimated by a factor of approximately 2, implicating that the OH + NO2 rate was overestimated by the same factor. This point is experimentally explored in the companion paper of Srinivasan et al. (next paper in this issue).     

Increased sensitivity of an enzyme immunoassay (ELISA) for the determination of triazine herbicides by variation of tracer incubation time

Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.Nomenclature ametryn 2-(ethylamino)-4-(isopropylamino)-6-(methylthio)-1,3,5-triazine - atrazine 2-(chloro)-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine - deethylatrazine 2-(amino)-4-(chloro)-6-(isopropylamino)-1,3,5-triazine - DMSO dimethylsulfoxide - DOC dissolved organic carbon - ELISA enzyme-linked immunosorbent assay - glyme 1,2-dimethoxyethane - hydroxyatrazine 2-(ethylamino)-4-(hydroxy)-6-(isopropylamino)-1,3,5-triazine - PBS phosphate buffered saline - propazine 2-(chloro)-4,6-bis(isopropylamino)-1,3,5-triazine - simazine 2-(chloro)-4,6-bis(ethylamino)-1,3,5-triazine - terbuthylazine 2-(tert-butylamino)-4-(chloro)-6-(ethylamino)-1,3,5-triazine - TLC thin-layer chromatography - TMB 3,3,5,5-tetramethylbenzidine - tracer enzyme (peroxidase) labeled hapten     

HPLC determination of andrographolide in rat whole blood: study on the pharmacokinetics of andrographolide incorporated in liposomes and tablets

A sensitive and simple high-performance liquid chromatographic method with UV detection was developed and validated for the determination of andrographolide in rat whole blood. Carbamazepine was employed as internal standard and the blood sample was extracted with chloroform. Chromatographic separations were achieved on a Chromasil ODS column (250 x 4.6 mm, 5 microm). The mobile phase was consisted of methanol-water (52:48, v/v) and delivered at 0.8 mL/min. The detection wavelength was set at 225 nm. The calibration curve had a good linearity in the range 0.053-530 microg/mL in rat whole blood with its correlation coefficient being 0.996. The extraction recovery of andrographolide was ranged from 65.7 to 72.6%. The intra-day and inter-days repeatabilities were below 4.2% in terms of the percentage of relative standard deviation (RSD). The method was used to provide data on the pharmacokinetics of the drug in rats. The data obtained was processed using the 3P87 pharmacokinetic program. The results showed that the disposition of andrographolide after intravenous administration of liposomal andrographolide conformed to a two-compartment open model with alpha = 4.75 x 10(-2) +/- 2.41 x 10(-3) min(-1), beta = 3.16 x 10(-3) +/- 1.58 x 10(-4) min(-1), V(c) = 174.67 +/- 13.97 mL, k(21) = 1.60 x 10(-2) +/- 8.12 x 10(-4) min(-1), k(10) = 9.38 x 10(-3) +/- 5.62 x 10(-4) min(-1), k(12) = 2.53 x 10(-2) +/- 1.27 x 10(-3) min(-1) and AUC(0-infinity) = 1525.47 +/- 92.35 microg min/mL. For the intragastric administration of andrographolide tablets, the disposition of andrographolide followed a one-compartment open model with k(e) = 6.78 x 10(-3) +/- 3.53 x 10(-4) min(-1), k(a) = 3.69 x 10(-2) +/- 4.68 x 10(-3) min(-1), T(max) = 59.69 +/- 3.61 min, C(max) = 1.62 +/- 0.11 microg/mL, V(c) = 1056.90 +/- 83.42 mL, AUC(0-infinity) = 348.75 +/- 24.41 microg min/mL.     

Lipase-catalyzed asymmetric synthesis of desprenyl-carquinostatin A and descycloavandulyl-lavanduquinocin

An asymmetric synthesis of the core carbazole structure, 6-desprenyl-carquinostatin 3 and 6-descycloavandulyl-lavanduquinocin 3, toward a total synthesis of carquinostatin A (1) and lavanduquinocin (2), has been established. Lipase QLM (Meito) catalyzed enantioselective acetylation of the racemic alcohol 6 gave the (-)-acetate 7 and the (+)-alcohol 6 with high enantioselectivity. The absolute stereochemistry of the (-)- and (+)-alcohol 6 have been determined to be R- and S-configurations, respectively, by the advanced Mosher method. In the same manner, the (-)-acetate 13 and the (+)-alcohol 12 have been obtained from the racemic alcohol 12. The (R)-(-)-acetate 13, derived from the (R)-(-)-acetate 7, was the same as the (-)-acetate 13, which has been determined to be (R)-configuration. Oxidation of the (R)-(-)-acetate 13 followed by hydrolysis afforded (R)-(-)-6-desprenyl-carquinostatin [and (R)-(-)-6-descycloavandulyl-lavanduquinocin] 3. In addition, oxidation of the (S)-(+)-alcohol 12 provided (S)-(+)-3, which is the enantiomer of 6-desprenyl-carquinostatin A (R)-(-)-3.     

Energetics of hydroxybenzoic acids and of the corresponding carboxyphenoxyl radicals. Intramolecular hydrogen bonding in 2-hydroxybenzoic acid

The energetics of the phenolic O-H bond in the three hydroxybenzoic acid isomers and of the intramolecular hydrogen O-H- - -O-C bond in 2-hydroxybenzoic acid, 2-OHBA, were investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of monoclinic 3- and 4-hydroxybenzoic acids, at 298.15 K, were determined as Delta(f)(3-OHBA, cr) = -593.9 +/- 2.0 kJ x mol(-1) and Delta(f)(4-OHBA, cr) = -597.2 +/- 1.4 kJ x mol(-1), by combustion calorimetry. Calvet drop-sublimation calorimetric measurements on monoclinic samples of 2-, 3-, and 4-OHBA, led to the following enthalpy of sublimation values at 298.15 K: Delta(sub)(2-OHBA) = 94.4 +/- 0.4 kJ x mol(-1), Delta(sub)(3-OHBA) = 118.3 +/- 1.1 kJ x mol(-1), and Delta(sub)(4-OHBA) = 117.0 +/- 0.5 kJ x mol(-1). From the obtained Delta(f)(cr) and Delta(sub) values and the previously reported enthalpy of formation of monoclinic 2-OHBA (-591.7 +/- 1.3 kJ x mol(-1)), it was possible to derive Delta(f)(2-OHBA, g) = -497.3 +/- 1.4 kJ x mol(-1), Delta(f)(3-OHBA, g) = -475.6 +/- 2.3 kJ x mol(-1), and Delta(f)(4-OHBA, cr) = -480.2 +/- 1.5 kJ x mol(-1). These values, together with the enthalpies of isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3PW91/aug-cc-pVDZ, MPW1PW91/aug-cc-pVDZ, and MPW1PW91/aug-cc-pVTZ) and the CBS-QMPW1 methods, were used to derive the enthalpies of formation of the gaseous 2-, 3-, and 4-carboxyphenoxyl radicals as (2-HOOCC(6)H(4)O(*), g) = -322.5 +/- 3.0 kJ.mol(-1) Delta(f)(3-HOOCC(6)H(4)O(*), g) = -310.0 +/- 3.0 kJ x mol(-1), and Delta(f)(4-HOOCC(6)H(4)O(*), g) = -318.2 +/- 3.0 kJ x mol(-1). The O-H bond dissociation enthalpies in 2-OHBA, 3-OHBA, and 4-OHBA were 392.8 +/- 3.3, 383.6 +/- 3.8, and 380.0 +/- 3.4 kJ x mol(-1), respectively. Finally, by using the ortho-para method, it was found that the H- - -O intramolecular hydrogen bond in the 2-carboxyphenoxyl radical is 25.7 kJ x mol(-1), which is ca. 6-9 kJ x mol(-1) above the one estimated in its parent (2-OHBA), viz. 20.2 kJ x mol(-1) (theoretical) or 17.1 +/- 2.1 kJ x mol(-1) (experimental).     

Expeditious asymmetric synthesis of a stereoheptad corresponding to the C(19)-C(27)-ansa chain of rifamycins: formal total synthesis of Rifamycin S

In the presence of sulfur dioxide and an acid promoter, (-)-(1E,3Z)-2-methyl-1-((1S)-1-phenylethoxy)penta-1,3-dien-3-yl isobutyrate reacts with (Z)-3-(trimethylsilyloxy)pent-2-ene giving a silyl sulfinate intermediate that undergoes, in the presence of palladium catalyst, a desilylation and retro-ene elimination of SO(2) with formation of (-)-(1Z,2S,3R,4S)-1-ethylidene-2,4-dimethyl-5-oxo-3-((1S)-1-phenylethoxy)-heptyl isobutyrate as major product. This ethyl ketone undergoes cross-aldol reaction with (2S)-2-methyl-3-[(tert-butyldimethylsilyl)oxy]propanal giving an aldol that is reduced into a stereoheptad corresponding to the C(19)-C(27)-segment of Rifamycins with high diastereoselectivity and enantiomeric excess.