Photophysical studies on antimalarial drugs

Most drugs used in the treatment of malaria produce phototoxic side effects in both the skin and the eye. Cutaneous and ocular effects that may be caused by light include changes in skin pigmentation, corneal opacity, cataract formation and other visual disturbances including irreversible retinal damage (retinopathy) leading to blindness. The mechanism for these reactions in humans is unknown. We irradiated a number of antimalarial drugs (amodiaquine, chloroquine, hydroxychloroquine, mefloquine, primaquine and quinacrine) with light (lambda > 300 nm) and conducted electron paramagnetic resonance (EPR) and laser flash photolysis studies to determine the possible active intermediates produced. Each antimalarial drug produced at least one EPR adduct with the spin-trap 5,5-dimethyl-1-pyrroline N-oxide in benzene: superoxide/hydroperoxyl adducts (chloroquine, mefloquine, quinacrine, amodiaquine and quinine), carbon-centered radical adducts (all but primaquine), or a nitrogen-centered radical adduct only (primaquine). In ethanol all drugs except primaquine produced some superoxide/hydroperoxyl adduct, with quinine, quinacrine, and hydroxychloroquine also producing the ethoxyl adduct. As detected with flash photolysis and steady-state techniques, mefloquine, quinine, amodiquine and a photoproduct of quinacrine produced singlet oxygen ([symbol: see text]delta = 0.38; [symbol: see text]delta = 0.36; [symbol: see text]delta = 0.011; [symbol: see text]delta = 0.013 in D2O, pD7), but only primaquine quenched singlet oxygen efficiently (2.6 x 10(8) M-1 s-1 in D2O, pD7). Because malaria is a disease most prevalent in regions of high light intensity, protective measures (clothing, sunblock, sunglasses or eye wraps) should be recommended when administering antimalarial drugs.     

Photoreactivity of biologically active compounds. XVI. Formation and reactivity of free radicals in mefloquine

The formation and reactivity of the triplet state and free radicals of mefloquine hydrochloride (MQ) have been investigated by pulse radiolysis and flash photolysis. The excited triplet, cation radical and anion radical have been produced and their absorption characteristics determined. The triplet-triplet absorption spectrum of MQ showed a maximum at 430 nm, with a molar absorption coefficient of 3600 M(-1) cm(-1) and the quantum yield for intersystem crossing was determined to be close to unity. Deactivation of the triplet, in the absence of oxygen, led to the formation of MQ cation and/or anion radicals. The molar absorption coefficient of the cation radical at 330 nm was determined to be 2300 M(-1) cm(-1), whilst that for the anion radical was 2400 M(-1) cm(-1) at 620 nm and 3600 M(-1) cm(-1) at 350 nm. The molar absorption coefficients of the proposed neutral radical at 320 nm and 520 nm were 4000 M(-1) cm(-1) and 1300 M(-1) cm(-1) respectively. The quantum yield for the formation of singlet oxygen, sensitized by MQ triplet, was determined to be close to unity. Aqueous solutions of MQ were found to photoionize to yield hydrated electron and cation radical of MQ in a biphotonic process. The influences of pH, buffer concentration, oxygen concentration and addition of sodium azide on the formation and reactivity of the transients were evaluated. The reactions between MQ and solvated electrons and superoxide anion were also studied.     

HPTLC-Bestimmung von Paracetamol im Serum

Ohne Zusammenfassung

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Determination of paracetamol in serum by HPTLC

     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).     

联苯胺分光光度法测定食盐中碘含量

基于在盐酸介质中,碘酸钾氧化联苯胺使其显色,提出了光度法测定食盐中微量碘的方法。在40℃的水浴中,当2 mol.L-1盐酸溶液用量为1.00 mL0、.42 g.L-1联苯胺溶液用量为0.80 mL时,方法的线性范围为100~1 400μg.L-1,最大吸收波长在425 nm处,表观摩尔吸光率为1.4×105L.mol-1.cm-1。用于测定加碘食盐中碘含量的测定,回收率在97.5%~101.2%之间,相对标准偏差(n=7)在0.9%~1.9%之间。