Survey of residual tetracyclines in kidneys of diseased animals in Aichi Prefecture, Japan (1985-1997)

A survey was conducted to determine the incidence of tetracycline antibiotic (TCAs) residues in the kidneys of slaughtered animals that did not pass inspection for human consumption by the Japanese Food Sanitation Law and the Meat Inspection Law at the slaughterhouses in Aichi Prefecture, Japan, from April 1985 to March 1998. The kidneys were analyzed by the AOAC Official Method 995.09. Among 424 animals (147 cattle and 277 pigs), 131 (30.9%) were contaminated with TCAs, including 69 (16.3%) with chlortetracycline (CTC), 61 (14.4%) with oxytetracycline (OTC), 3 (0.7%) with tetracycline (TC), and 1 (0.2%) with doxycycline (DC). One sample (cattle kidney) was contaminated with both OTC and DC. The frequencies of OTC and TC residues were significantly higher (p < 0.05) in cattle than in pigs, whereas, the frequency of CTC was significantly higher (p < 0.01) in pigs. Pig kidney samples collected in 1991-1997 had significantly higher incidences of TCAs and CTC (p < 0.01) residues than those in 1985-1986.     

Pesticide residues in agricultural products monitored in Hyogo Prefecture,Japan, FYs 1995-1999

During a 5-year monitoring survey (April 1995-March 2000) of pesticide residues in agricultural products, 765 samples (478 domestic; 287 imported) collected in Hyogo Prefecture, Japan, were analyzed. The number of pesticides tested increased from 107 in fiscal year (FY) 1995 to 204 in FY 1999. The purpose of the study was to promote consumer safety by excluding the food illegally containing pesticide residues from markets. Overall, 51 % of domestic and 32% of imported samples contained no detectable residues. Multiple residues were detected in 152 (32%) of domestic and 146 (51%) of imported samples. The limit of quantitation was set at 0.01 microg/g and the limit of detection was 0.001 microg/g. Most of the residues were present at low concentrations; 70% of detections in domestic samples were <0.05 microg/g, and 97% were <0.5 microg/g. Although 86% of antifungal agent residues in imported citrus fruits were > or = 0.1 microg/g, 59% of the other residues in imported samples were <0.05 microg/g, and 96% were <0.5 microg/g. Violations of maximum residue limits (MRL) were observed in 3 samples: diazinon in chrysanthemums, dieldrin in cucumbers, and bitertanol in bananas. Of the detectable residues above 0.01 microg/g, 55% in domestic and 38% in imported samples were <10% of the MRL. Of all the samples, 2.4% contained more than 5 different pesticides; tomatoes, strawberries, apples, and citrus fruits tended to have more multiple residues.     

Copper(II) acetate and picrate complexes of sulfa drugs

Summary Copper(II) acetate and picrate complexes of sulfa drugsviz., sulfanilamide, sulfaguanidine, sulfathiazole, sulfadiazine, sulfamerazine and sulfamethazine were prepared and characterized with the help of analytical, electronic, i.r. and magnetic moment data. The complexes are paramagnetic, planar or mixed planar and octahedral, insoluble and melt (with decomposition) in the 185°–225° range. The sulfa drugs coordinate through their amino groups and the acetate or picrate ions are bonded to the metal through the -C(O)O group.     

Organotin(IV) complexes of Schiff bases derived by condensation of heterocyclic ketones and sulfa drugs

Abstract —Reaction of bis(triorganotin)oxide with Schiff bases derived by condensation of heterocyclic ketones, 2-acetylfuran and 2-acetylthiophene, with various sulfadrugs (sulfaguanidine, sulfathiazole, sulfisoxazole and sulfadiazine) leads to the formation of a new series of organotin(IV) complexes. An attempt has been made to probe their structures on the basis of elemental analysis, conductance measurements, molecular weight determination, UV, IR and NMR (1H, 13C and 119Sn) spectral studies. The results of antimicrobial effects of some representative complexes on different species of pathogenic fungi and bacteria have also been recorded and discussed.     

A new,sensitive, and rapid spectrophotometric method for the determination of sulfa drugs

A sensitive, rapid, and simple spectrophotometric method is described for the determination of sulfa drugs. The method is based on the formation of a red-colored product by the diazotization of sulfonamides such as sulfathiazole (SFT), sulfadiazine (SFD), sulfacetamide (SFA), sulfamethoxazole (SFMx), sulfamerazine (SFMr), sulfaguanidine (SFG), and sulfamethazine (SFMt), followed by complexation with dopamine in the presence of molybdate ions in (1 + 1) H2SO4 medium. Absorbance of the resulting red product is measured at 490-510 nm, and the product is stable for 2 days at 27 degrees C. Beer's law is obeyed in the concentration range of 0.04-8.0 microg/mL at the wavelength of maximum absorption. The method was used successfully for the determination of some sulfonamides in tablets and eye drops. Common excipients used as additives in pharmaceuticals do not interfere in the proposed method. The method offers the advantages of simplicity, rapidity, and sensitivity without the need for extraction or heating. The limits of detection and quantitation were calculated for SFT, SFD, SFA, SFMx, SFMr, SFG, and SFMt.     

Pre-column derivatization of sulfa drugs with fluorescamine and high-performance liquid chromatographic determination at their residual levels in meat and meat products.

A rapid, sensitive and selective high-performance liquid chromatographic method is described for simultaneous determination of eight sulfa drugs in meat and meat products using pre-column derivatization with fluorescamine. The drugs are sulfisomidine, sulfadiazine, sulfamerazine, sulfadimidine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline. The method includes blender extraction of 3-g samples with chloroform, partition with 3 M hydrochloric acid, derivatization with fluorescamine at pH 3.0 and subsequent high-performance liquid chromatographic analysis on a C18 column with fluorescence detection at an excitation wavelength of 405 nm and an emission wavelength of 495 nm. The drugs were separated with a mobile phase of acetonitrile-2% acetic acid (3:5) at 55 degrees C. The average recovery from samples fortified at 0.1 ng/g was 92.6% with a coefficient of variation of 6.2%. The detection limit was 0.01 ng/g for sulfaquinoxaline and 0.005 ng/g for the other seven drugs. The method was field-tested in a survey of 37 samples including beef (five), pork (seven), chicken (seven), ham (five), sausage (eight), bacon (two) and roast beef (three). Sulfadimidine was detected in one pork sample at the level of 0.295 ng/g and in ham at 0.178 ng/g.     

Interaction of hexafluorosilicic acid with sulfa drugs. Bis(sulfathiazolium) hexafluorosilicate: Spectral data and crystal structure

Interaction of hexafluorosilicic acid with sulfa drugs sulfathiazole (stz) and sulfalen (2-sulfanilamido-3-methoxypyrazine, sl) results in the crystalline salts of the compositions [stzH]₂[SiF₆] (I) and [4-H₂NO₂SPhNH₃]₂[SiF₆] (II). Complex I is characterized by IR, mass spectrometry data and single crystal X-ray diffraction. The crystal structure of I is stabilized by a network of charge-assisted hydrogen bonding. The relationship between the solubility and H-bonding system in I, II and related “onium” hexafluorosilicates is discussed. The formation of complex II, previously reported as an interaction product of hexafluorosilicic acid with 4-aminobenzenesulfonamide (sulfanilamide), is the result of cleavage of the C-N bond in sulfalen in acidic medium.     

Acetylacetone-formaldehyde reagent for the spectrophotometric determination of some sulfa drugs in pure and dosage forms

A new simple and sensitive spectrophotometric procedure for the determination of sulfacetamide sodium (I), sulfadiazine (II), sulfadimidine (III) and sulfathiazole (IV) is based on the reaction of the drug with acetylacetone-formaldehyde reagent to give a yellow product having _max at 400 nm. Optimization of the reaction conditions has been investigated. A linear correlation was obtained between absorbance at _max and the concentration. The Beer's law limits of I, II, III and IV are 4–80, 4–72, 4–60 and 4–80 g/ml, respectively. For more accurate results, Ringbom optimum concentration ranges were evaluated to be 6–76, 8–66, 6–56 and 8–75 g/ml for I, II, III and IV, respectively. The molar absorptivities and Sandell sensitivities for all sulfa drugs under consideration were evaluated. Relative standard deviations of 0.98, 1.07, 0.86 and 0.79% were obtained for I, II, III and IV, respectively. The method has been compared to the official method and found to be simple, accurate (t-test) and reproducible (F-test). The developed procedures were applied for bulk sulfa drugs and some of their dosage forms without interferences from additive and common prescribed drugs.     

Advances ofcapillary electrophoresis in clinical and forensic analysis (1999-2000)

In this paper, capillary electrophoresis in clinical and forensic analysis is reviewed on the basis of the literature of 1999, 2000 and the first papers in 2001. An overview of progress relevant examples for each major field of application, namely (i) analysis of drug seizures, explosives residues, gunshot residues and inks, (ii) monitoring of drugs, endogenous small molecules and ions in biofluids and tissues, (iii) general screening for serum proteins and analysis of specific proteins (carbohydrate deficient transferrin, alpha1-antitrypsin, lipoproteins and hemoglobins) in biological fluids, and (iv) analysis of nucleic acids and oligonucleotides in biological samples, including oligonucleotide therapeutics, are presented.     

Total synthesis of chlorinated phenylpyrrole antibiotics, (+)- and (−)-neopyrrolomycins

(+)- and (−)-Neopyrrolomycins have been synthesized from 3,5-dichlorophenol through regioselective halogenations and optical resolution.     

Polyene macrolide antibiotics: Mechanisms of inactivation,ways of stabilization,and methods of disposal of unusable drugs (Review)

Published data concerning various mechanisms of the inactivation of polyene macrolide antibiotics, ways of their stabilization, and search for new stable dosage forms prepared with the use of nanotechnology techniques were summarized. Environmentally acceptable ways of disposal of pharmaceutical waste, and in particular polyene macrolide antibiotics, were discussed.     

Imposex in Sea Snails,Caused by Organotin (Tributyltin and Triphenyltin) Pollution in Japan: a Survey

A country-wide survey and laboratory experiments on imposex (a superimposition of male sex organs on female sea snails) in Japanese sea snails were carried out: 38 species were observed to be affected by imposex. For the rock shell, Thais clavigera , the percentage occurrence of imposex was 100% at almost all sites surveyed. The degree of imposex seemed to be positively correlated with the concentrations of tributyltin (TBT) and triphenyltin (TPT) in the species. The results of laboratory experiments showed that imposex in T. clavigera was initiated and promoted by both TBT and TPT. Many oviduct-blocked individuals, which were thought to be sterile, were observed in T. clavigera at sites near marinas and harbours. The effects of organotin pollution on the population of T. clavigera were observed at the sites near marinas. From the results of the additional country-wide survey on imposex in T. clavigera during 1993–1995, serious organotin pollution and imposex symptoms in the species are still continuing in Japan. © 1997 by John Wiley & Sons, Ltd.     

Asymmetric syntheses of the homalium alkaloids (-)-(s,s)-homaline and (-)-(r,r)-hopromine

The highly diastereoselective conjugate additions of the novel lithium amide reagents lithium (R)-N-(3-chloropropyl)-N-(α-methylbenzyl)amide and lithium (R)-N-(3-chloropropyl)-N-(α-methyl-p-methoxybenzyl)amide to α,β-unsaturated esters were used as the key steps in syntheses of the homalium alkaloids (-)-(S,S)-homaline and (-)-(R,R)-hopromine. The asymmetric synthesis of (-)-(S,S)-homaline was achieved in 8 steps and 18% overall yield, and the asymmetric synthesis of (-)-(R,R)-hopromine was achieved in 9 steps and 23% overall yield, from commercially available starting materials in each case. These syntheses therefore represent by far the most efficient total asymmetric syntheses of these alkaloids reported to date. A sample of the (4'R,4'S)-epimer of hopromine was also produced using this approach, which provided the first unambiguous confirmation of its absolute configuration and therefore that of natural (-)-(R,R)-hopromine.     

Synthesis of (-)-matairesinol, (-)-enterolactone,and (-)-enterodiol from the natural lignan hydroxymatairesinol

[reaction: see text] We describe here a four-step semisynthetic method for the preparation of enantiomerically pure (-)-enterolactone starting from the readily available lignan hydroxymatairesinol from Norway spruce (Picea abies). Hydroxymatairesinol was first hydrogenated to matairesinol. Matairesinol was esterified to afford the matairesinyl 4,4'-bistriflate, which was deoxygenated by palladium-catalyzed reduction to 3,3'-dimethylenterolactone. Demethylation of 3,3'-dimethylenterolactone and reduction with LiAlH(4) yielded (-)-enterolactone and (-)-enterodiol, respectively.