High-performance liquid chromatography with post-column derivatisation and fluorescence detection for sensitive determination of aflatoxin M1 in milk and cheese

A new HPLC method with fluorescence detection using pyridinium hydrobromide perbromide as a post-column derivatising agent has been developed to determine aflatoxin M1 in milk and cheese. The detection limits were 1 ng/kg for milk and 5 ng/kg for cheese. The calibration curve was linear from 0.001 to 0.1 ng injected. The method includes a preliminary C18-SPE clean-up and the average recoveries of Aflatoxin M1 from milk and cheese, spiked at levels of 25-75 ng/kg and 100-300 ng/kg, respectively, were 90 and 76%; the precision (RSDr) ranged from 1.7 to 2.6% for milk and from 3.5 to 6.5% for cheese. The method is rapid, easily automatable and therefore useful for accurate and precise screening of aflatoxin M1 in milk and cheese.     

DMF-甲醇体系粘度与核磁共振化学位移的同时关联

提出了一个基于局部组成概念上的核磁共振模型. 利用该模型和以前别人提出的局部组成型粘度方程, 成功地同时关联属于传递性质的粘度数据和属于波谱性质的核磁共振化学位移数据，关联所得到化学位移的平均绝对偏差小于0.0072，粘度的平均绝对偏差小于0.0006 mPa•s，结果表明提出的局部组成模型是合理的.     

VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE

Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H₂O₂. The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H₂O₂, suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains.     

Determination of the substituent effect on the O-H bond dissociation enthalpies of phenolic antioxidants by the EPR radical equilibration technique

The bond dissociation enthalpies (BDE) of several phenols containing electron-withdrawing substituents in the para position have been determined by means of the EPR radical equilibration technique. It has been found that CN, NO(2), CHO, COOR, and COOH induce an increase of the BDE value of the O-H bond, thus producing a worsening of the antioxidant activity of phenols, while Cl, Ph, and CH[double bond]CHPh show an opposite effect. The contributions of these substituents for the calculation of the BDE values in polysubstituted phenols by using the group additivity rule have also been derived. It is shown that this rule provides quite reliable predictions of bond strengths, so that the method can be conveniently used to estimate new data on substituted phenols.     

氢部分选择性催化还原NO反应研究

在低钯含量活性非均布Pd/Al2O3催化剂上，实现了富氧条件下，氢部分选择性催化还原NO过程，低温、富氧条件下NO的转化率高达80％－100％。NO直接分解实验表明，600℃，NO分解转化率在无氧时为17．3％，有0．5％氧存在时接近于0。氢非选择性还原NO条件下，100℃以下，NO转化率为100％。根据实验结果及文献，推测了氢部分选择性还原NO过程中可能存在的反应，不同的反应温度下，NO脱除反应有所不同。在115℃以下，NO还原产物为NH3；115℃－155℃，NO还原产物为NH3、N2O和N2；155℃以上，NO还原产物中无NH3存在。NO还原反应与氢氧反应是平行的竞争反应。     

The replacement of five-membered N-donor heterocycles from aminotrichlorogold(III) complexes. A comparison with pyridines

The kinetics of the process AuCl₃(nu) + Cl⁻→ AuCl ₄ ⁻ + nu (nu = one of a number of five-membered N-donor heterocycles covering a wide range of basicity, namely: oxazole, 2,4,5-trimethyloxazole, thiazole, 5-methylthiazole, 4-methylthiazole, 4,5-dimethylthiazole, 2,4-dimethylthiazole, 2,4,5-trimethylthiazole, imidazole and 2-methylimidazole) have been studied in methanol at 25 °C. The reactions follow the usual two-term rate law, rate = (k ₁ + k ₂[Cl⁻])[complex], observed in a square-planar substitution associative-mechanism. The second-order rate constants, k ₂, indicate that the discriminating ability of Au^(III) in these complexes is good and markedly influenced by the nature of the leaving group. A linear-free-energy relationship, logk ₂ = 0.53pK _a + constant, is observed between the rate constant and the basicity of the leaving group for its replacement by chloride. The results are compared with data from the literature regarding a series of complexes of the type AuCl₃(py) (py = one of a number of pyridines) reacting with the Cl⁻ anion under the same experimental conditions. The reactivity depends not only upon ligand basicity but also upon the nature of the ligand in the order: pyridines> five-membered heterocycles. Steric factor due to the presence of a single methyl group ortho to the sp² nitrogen atom in the ring has no influence on the rate of substitution while, surprisingly, when there are two ortho methyl groups a remarkable steric retardation effect is observable. The results are discussed in terms of reaction-profile in the associative-substitution reaction and bonding interactions in the ground and transition states.     

Zinc(II) as an allosteric regulator of liposomal membrane permeability induced by synthetic template-assembled tripodal polypeptides

Three copies of peptide sequences from the peptaibol family, known to affect the permeability of the lipid bilayer of membranes, were connected to tris(2-aminoethyl)amine (TREN), a tripodal metal ion ligand, to prepare functional peptides capable of modifying the permeability of liposomal membranes. Some of the resulting tripodal polypeptide derivatives are very effective in promoting carboxyfluorescein (CF) leakage from CF-loaded unilamellar vesicles composed of a 70:30 phosphatidylcholine/cholesterol blend. The activity of these novel compounds was shown to be tunable upon metal ion coordination of the TREN subunit; the tripodal apopeptide was far more effective than its ZnII complex. Leakage experiments showed that a minimum number of five amino acids per peptide chain is required to form active systems. A mechanism is proposed in which the ZnII ion changes the conformation of the template from extended to globular and thus acts as an allosteric regulator of the activity of the systems. Molecular modeling studies indicate that when the three peptide chains are connected to the template in the extended conformation, the resulting tripodal polypeptide is able to span across the membrane, thus allowing the formation of permeable channels made of a cluster of molecules. The same change of conformation induces, to some extent, fusion of the membranes of different liposomes.     

Proton controlled intramolecular communication in dinuclear ruthenium(II) polypyridine complexes

The synthesis and characterization of two dinuclear ruthenium polypyridyl complexes based on the bridging ligands 5,5'-bis(pyridin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and 5,5'-bis(pyrazin-2' '-yl)-3,3'-bis(1H-1,2,4-triazole) and of their mononuclear precursors are reported. The dinuclear compounds have been prepared by a Ni(0) catalyzed coupling of a mononuclear ruthenium(II) polypyridyl complex containing a brominated triazole moiety. Electrochemical and photophysical studies indicate that, in these dinuclear complexes, the protonation state of the bridge may be used to tune the intercomponent interaction between the two metal centers and that these species act as proton driven three-way molecular switches that can be read by electrochemical or luminescence techniques.     

Mono- and dihydryl-pentafluorosulfur-F-alkanes [1]

The systematic preparation of partially fluorinated pentafluorosulfur alkanes containing no additional halogens is reported. Thus, the indirect addition of “HF” (via KF/formamide) to SF₅CH=CF₂, SF₅CFCF₂, and SF₅C(CF₃)CF₂ produces SF₅CH(in2)CF₃, SF₅CHFCF₃, and SF₅C(CF₃)₂H respectively. The monohydryl-pentafluorosulfur-F- alkanes react readily with S₂O₆F₂ to form the corresponding fluorosulfates by oxidative displacement of hydrogen, while the dihydryl derivative undergoes cleavage to produce F-acetyl fluoride. Efforts to convert some of the new materials to the important but unknown pentafluorosulfur “ketone,” SF₅C(O)CF₃, were unsuccessful.     

Chronocoulometric study of the electrochemistry of Prussian blue

During the electrochemical oxidation of Prussian blue (PB) to Prussian yellow (PY), an electrocatalytic oxygen production proceeds at the electrode when aqueous electrolyte solutions are used. The formed oxygen is scavenged by the PY, probably by absorption, and it is consumed during the electrochemical reduction of PY to PB by a heterogeneous chemical reaction of PB with oxygen to PY and hydrogen peroxide. Because of this catalytic regeneration of PY, it is impossible to determine the amount of low-spin iron by chronocoulometry using a potential program in which PB is first oxidized to PY and then the charge is measured to reduce PY to PB. The latter charge is biased by the electrocatalytic PY regeneration.