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EN
The popular pharmaceutical base used in pharmacy – vaselinum flavum – was studied by an X-band (9.3 GHz) EPR spectrometer in the range of microwave power of 2.2–70 mW. The samples were sterilized in hot air oven at temperatures: 160°C (120 min), 170°C (60 min), and 180°C (30 min). The aim of this work was to determine properties and free radical concentrations in vaselinum flavum thermally sterilized at different conditions. The changes in free radical system in vaselinum flavum during storage were analyzed. Free radicals were found in all the heated samples. The lowest free radical concentration was obtained for vaselinum flavum heated at 180°C for 30 min; so these parameters are proposed for the thermal sterilization of this pharmaceutical base. Interactions with oxygen decreased free radical concentration in vaselinum flavum during storage. Strong quenching of free radicals in vaselinum flavum was observed after 2 days for the samples sterilized at temperatures 160 and 180°C. Such an effect for vaselinum flavum heated at temperature 170°C was observed later, 13 days after sterilization. Fast spin-lattice relaxation processes exist in thermally sterilized vaselinum flavum. The EPR lines of heated vaselinum flavum were homogeneously broadened. EPR spectroscopy and its use for examining the thermal sterilization process in pharmacy was confirmed.
EN
Free radicals in synthetic melanin and melanin from Sepia officinalis were studied by electron paramagnetic resonance (EPR) spectroscopy. The effect of time of ultraviolet (UV) irradiation on free radicals in these melanins was tested. The samples were exposed to UV during 15, 30, and 60 minutes. EPR spectra were measured with microwaves from an X-band (9.3 GHz) in the range of microwave power of 2.2–70 mW. The performed EPR examinations indicate that high concentrations (~1021–1022 spin/g) of o-semiquinone free radicals with g factors of 2.0039–2.0045 exist in all the tested samples. For nonirradiated samples, free radical concentration was higher in natural melanin than in synthetic melanin. UV irradiation caused the increase of free radical concentrations in synthetic melanin samples and this effect depends on the time of irradiation. The largest free radical formation in the both melanins was obtained for 60 min of UV irradiation. Free radical concentrations after the UV irradiation of melanins during 30 min were lower than during irradiation by 15 min, and probably this effect was the result of recombination of the radiatively formed free radicals. EPR lines of the tested samples broadened with increasing microwave power, so these lines were homogeneously broadened. The two types of melanins differed in the time of spin-lattice relaxation processes. Slower spin-lattice relaxation processes exist in melanin from Sepia officinalis than in synthetic melanin. UV irradiation did not change the time of spin-lattice relaxation processes in the tested melanins. The performed studies confirmed the usefulness of EPR spectroscopy in cosmetology and medicine.
EN
Free radicals formed during thermal sterilization of eucerinum anhydricum – the pharmaceutical base were examined by an X-band (9.3 GHz) spectrometer. Eucerinum anhydricum was sterilized at different physical conditions according to the Polish Pharmacopeia norms. The samples were heated at temperatures: 160°C (120 min), 170°C (60 min), and 180°C (30 min). The aim of this study is to compare free radical concentration and effect of microwave power on EPR spectra of eucerinum anhydricum base thermally sterilized at different temperatures and periods of time. The effect of time storage on the free radicals in the heated samples was tested. Free radical concentrations in the sample stored 15 min strongly decreased with the increasing of sterilization temperature, probably as the result of recombination. Storage caused strong decrease of free radical concentrations in the samples, probably as the result of interactions with oxygen. It was observed to be independent of sterilization conditions from 2 days of storage and longer. Because of the lowest free radical concentration, for eucerinum anhydricum thermal sterilization at 180°C for 30 min is recommended. The sterilized samples should be stored at inert atmosphere without oxygen molecules. Fast spin-lattice relaxation processes existed in sterilized eucerinum anhydricum. The character of changes of amplitudes and linewidths of EPR lines with increasing of microwave power was the same for different storage times. The parameters of thermal sterilization and storage time influenced free radical concentration in eucerinum anhydricum, but magnetic spin-lattice interactions were unchanged. The usefulness of EPR spectroscopy in optimization of thermal sterilization process of eucerinum anhydricum was confirmed.
EN
Paramagnetic centers in the two exemplary synthetic and natural dental biocompatible materials applied in implantology were examined by the use of an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra were measured in the range of microwave power 2.2–70 mW. The aims of this work were to compare paramagnetic centers concentrations in different dental biocompatible materials and to determine the effect of microwave power on parameters of their EPR spectra. It is the very fi rst and innovatory examination of paramagnetic centers in these materials. It was pointed out that paramagnetic centers existed in both natural (~1018 spin/g) and synthetic (~1019 spin/g) dental biocompatible materials, but the lower free radical concentration characterized the natural sample. Continuous microwave saturation of EPR spectra indicated that faster spin-lattice relaxation processes existed in synthetic dental biocompatible materials than in natural material. Linewidths (ΔBpp) of the EPR spectra of the natural dental material slightly increased for the higher microwave powers. Such effect was not observed for the synthetic material. The broad EPR lines (ΔBpp): 2.4 mT, 3.9 mT, were measured for the natural and synthetic dental materials, respectively. Probably strong dipolar interactions between paramagnetic centers in the studied samples may be responsible for their line broadening. EPR spectroscopy is the useful experimental method in the examination of paramagnetic centers in dental biocompatible materials.
EN
Free radicals formation in thermally sterilized famotidine was studied by the use of an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. The influence of temperature and time of sterilization on free radicals generated in famotidine was determined. The best sterilization conditions for the tested drug were found. Sterilization was done according to the pharmaceutical norms at temperatures 160°C (120 min), 170°C (60 min), and 180°C (30 min). It was pointed out that the optimal temperature of thermal sterilization for famotidine was 170°C and time of heating 60 min in this conditions the lowest free radicals concentration was found. The highest free radicals concentration was measured in famotidine heated at 160°C during 120 min, the long time of sterilization is responsible for this effect. Free radicals concentration changes during storage of famotidine after thermal sterilization. Its value increased with storage time for the drug sterilized at both temperatures of 170°C and 180°C. Free radicals concentration decreases from 7 days after sterilization. Complex system of free radicals with the shape of EPR lines, dependent on microwave power exist in thermally sterilized famotidine. Slow spin-lattice relaxation processes, strong dipolar interactions characterize thermally sterilized famotidine. Microwave saturation indicates that EPR lines of famotidine are homogeneously broadened. The usefulness of EPR spectroscopy to examine of the sterilized drugs was evaluated.
EN
Free radicals in Cladosporium cladosporioides cultured with amphotericin B were spectroscopically studied. The effect of drug concentrations on free radicals in the fungal melanin biopolymer was examined. It was pointed out that the concentrations of free radicals in the complexes of Cladosporium cladosporioides mycelium with amphotericin B depend on the drug concentrations. Eumelanin dominates in the fungal studied samples. The slow spin-lattice relaxation processes exist in the tested samples. Free radicals take a part in the formation of Cladosporium cladosporioides mycelium complexes with amphotericin B.
EN
Electron paramagnetic resonance (EPR) spectra of the model eumelanin – DOPA-melanin complexes with netilmicin measured with a microwave power in the range 0.3–200 mW were examined. The influence of microwave power on amplitudes (A) and linewidths (ΔBpp) of the spectra was determined. The EPR spectra were recorded by a BRUKER spectrometer at temperatures 125, 175, 225 and 275 K. Continuous microwave saturation of EPR lines was used to compare the acceleration of spin-lattice relaxation processes in melanin samples. Changes of the parameters of the EPR spectra of DOPA-melanin-netilmicin complexes, with the microwave power for the samples differing in netilmicin concentrations, were observed. The effect of temperature on the changes of the EPR spectra of the analyzed melanin complexes with the microwave power was determined. The spin-lattice relaxation is faster at higher temperatures for all the tested melanin complexes.
EN
Electron paramagnetic resonance spectroscopy at X-band (9.3 GHz) is used as the tool of optimalization of storage of thermally sterilized aminoglycoside antibiotic - streptomycin. Thermal sterilization at different conditions was performed according to the norms. Changes in free radicals system of this drug during storage after sterilization were detected. Lineshape analysis and microwave saturation of EPR spectra were done. Free radical concentrations were determined. Microwave saturation EPR analysis is proposed as useful method to determine the best conditions of storage of sterilized drugs.
PL
W pracy przedstawiono znane z literatury naukowej materiały węglowe, które mogą być stosowane jako sondy tlenometryczne w biologii i medycynie. Scharakteryzowano właściwości ich centrów paramagnetycznych oraz oddziaływania z paramagnetycznym tlenem O,. Paramagnetyczne są węgle naturalne, macerały, karbonizaty węgli i materiałów roślinnych. Jako sondy tonometrycz-ne stosujemy materiały węglowe zawierające dużą ilość centrów paramagnetycznych oraz wielopierścieniowe struktury aromatyczne. Parametry linii EPR sond węglowych silnie zależą od koncentracji tlenu w otoczeniu próbki.
EN
In this work we present coal materials known from literaturę, which may be used as oximettic probes in biology and medicine. Properties of their paramagnetic centers and interactions with paramagnetic oxygen O, were characterized. Paramagnetic are natural coals, macerals, carbonizates of coal and plant materials. Coal materials containing high amount of paramagnetic centers and multi-ring aromatic units are used as oximetric probes. Parameters of EPR lines of coal probes strongly depend on oxygen concentration in sample environment.
PL
Przeprowadzono badania wolnych rodników powstających w diklofenaku podczas ogrzewania w temperaturze 180°C. Jako technikę badawczą zastosowano spektroskopię elektronowego rezonansu paramagnetycznego (EPR). Dla wyjściowej próbki diklofenaku nie poddanego obróbce termicznej nie obserwowano widm EPR. Asymetryczne linie EPR rejestrowano natomiast w przypadku ogrzewanego diklofenaku. Zbadano wpływ czasu przechowywania na właściwości i koncentrację wolnych rodników w ogrzewanym diklofenaku. Stwierdzono, że w diklofenaku poddanym obróbce termicznej występuje duża ilość wolnych rodników (∼10(19) spin/g). Koncentracja wolnych rodników w ogrzewanym diklofenaku rośnie podczas przechowywania próbki. Oddziaływania wolne rodniki - tkanki mogą być odpowiedzialne za efekty toksyczne w organizmie oraz zmiany struktury biomateriałów. Obróbkę termiczną w przypadku diklofenaku należy więc odrzucić jako metodę sterylizacji leku. W pracy opisano wpływ mocy mikrofalowej na kształt, amplitudę i szerokość linii EPR dikofenaku. Metodą ciągłego nasycenia mikrofalowego linii EPR wykazano, że w diklofenaku zachodzą wolne procesy relaksacji spin-sieć.
EN
Electron paramagnetic resonance (EPR) examinations of free radicals formed in diclofenac heated at 180°C were performed. EPR spectrum for the non-heated sample was not obtained. Asymmetrical EPR lines were measured for the studied heated drug. Properties and free radicals concentration in heated diclofenac during storage of the sample were studied. High amount of free radicals (∼10(19) spin/g) characterizes diclofenac after heating of the sample. Free radicals concentration in heated diclofenac increases with increasing storage time of the sample. Free radicals - tissues interactions may be accompanied by toxic effects in organisms and changes of biomaterial's structure, so thermal sterilization is rather rejected as sterlization process for diclofenac. Influence of microwave power on lineshape, amplitudes and linewidth of EPR spectra was described. Continuous microwave saturation of EPR lines points out that slow spin-lattice relaxation processes exist in the heated diclofenac.
PL
Zbadano właściwości paramagnetyczne upigmentowanych grzybów glebowych Cladosporium cladosporioides oraz ich kompleksów z flucytozyną z zastosowaniem spektroskopii EPR. Eumelanina występująca w Cladosporium cladosporioides odpowiada głównie za ich silne sygnały EPR. Flucytozyna zwiększa koncentrację o-semichinonowych wolnych rodników w melaninie Cl. cladosporioides. Wolne procesy relaksacji spin-sieć zachodzą w Cladosporium cladosporioides.
EN
Paramagnetic properties of pigmented soil fungi Cladosporium cladosporioides and their complexes with flucytosine were studied by EPR spectroscopy. Eumelanin of Cladosporium cladosporioides is mainly responsible for their strong EPR signals. Flucytosine increases o-semiquinone free radicals concentration in melanin of Cl. cladosporioides. Slow spin-lattice relaxation processes exist in Cladosporium cladosporioides.
13
Content available Wolne rodniki w sterylizowanym termicznie verapamilu
PL
Zbadano generowanie wolnych rodników w werapamilu podczas sterylizacji termiczne w temperaturze 180 stopni C. Koncentrację i właściwości wolnych rodników analizowano z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego (EPR) na pasmo X (9.3 GHz). Wykazano, że w procesie sterylizacji termicznej powstają w werapamilu stabilne wolne rodniki. Wolne procesy relaksacji spin-sieć oraz silne oddziaływania dipolowe występują w werapamilu. Badania metodą EPR wykazały, że sterylizacja wysokotemperaturowa nie jest zalecana dla werapamilu.
EN
Free radical formation in verapamil during thermal sterilization at temperature 180 degrees of C was studied. Concentration and properties of free radicals were examined by the use of electron paramagnetic resonance (EPR) spectroscopy at X-band (9.3GHz). It was stated that stable free radicals are formed during thermal sterilization of verapamil. Slow spin-lattice relaxation processes and strong dipolar interactions exist in verapamil.EPR studies showed that sterilization at high temperature is not recommended for verapamil.
14
Content available Właściwości paramagnetyczne biomateriałów
PL
Paramagnetyczne biomateriały mogą być wysoce reaktywne oraz mogą ulegać destrukcji w wyniku reakcji wolnorodnikowych. W pracy przedstawiono znane z literatury naukowej badania właściwości paramagnetycznych biomateriałów z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego (EPR). Wskazano także paramagnetyczne biomateriały, które nie były dotąd analizowane metodą EPR.
EN
Paramagnetic biomaterials may be very reactive and they may be destroyed by free radical reactions. In this work the known from scientific publications electron paramagnetic resonance (EPR) studies of paramagnetic properties of biomaterials are presented. Unexamined by EPR paramagnetic biomaterials were also described.
PL
Wykonano badania wolnych rodników generowanych w monazotanie izosorbitolu pod wpływem wysokiej temperatury. Wyznaczono metodą elektronowego rezonansu paramagnetycznego (EPR) koncentrację wolnych rodników w próbce. Zbadano wpływ mocy mikrofalowej na kształt widm EPR monoazotanu izosorbitolu. Analizowano procesy relaksacji spin-spin i spin-sieć. Określono wpływ czasu przechowywania próbki po rozkładzie termicznym na wolne rodniki w leku.
EN
Studies of free radicals formed in isosorbide mononitrate upon high temperature were performed.. Free radical concentration in the sample was determined by electron paramagnetic resonance (EPR) method. Influence of microwave power on lineshape of EPR spectra of isisorbide mononitrate was examined. Spin-spin and spin-lattice relaxation proccesses were analysed. The effect of storage time of the sample on free radicals in the drug was determined.
PL
Sterylność substancji leczniczej jest niezwykle istot-na z punktu widzenia bezpieczeństwa farmakoterapii. Sterylizacja leków może powodować powstawanie wolnych rodników. Porównano właściwości wolnych rodników powstających pod wpływem promieniowania termicznego (180°C/30 minut) i promieniowania gamma (25kGy) w streptomycynie. Badania prze-prowadzono przy użyciu techniki elektronowego rezonansu paramagnetycznego EPR na pasmo X. Zarówno dla próbek sterylizowanych termicznie jak i radiacyjnie zarejestrowano szerokie linie EPR. Obydwie metody sterylizacji prowadzą do powstania wysokich koncentracji wolnych rodników (1016–1018 spin/g). Porównanie parametrów linii EPR dla sterylizacji termicznej i radiacyjnej wskazuje na podobne właściwości wolnych rodników w sterylizowanej próbce – niesparowane elektrony zlokalizowane na atomie tlenu. Więcej wolnych rodników, w przypadku zastosowanych parametrów sterylizacji, powstaje w próbkach sterylizowanych radiacyjnie.
EN
Sterility of medical substances plays significant role from the point of view of pharmacotherapy safety. Drugs sterilization can cause free radicals forming. It was compared free radicals properties forming in streptomycin under the influence thermal radiation (180°C/30 minutes) and gamma radiation (25kGy). Presented studies were performed by use of X band electron paramagnetic spectrometer. Both for thermal sterilized samples as well as for radiosterilized broad EPR lines were recorded. Both methods of sterilization lead to forming of high concentrations of free radicals (1016–1018spin/g). Comparing of EPR lines parameters for thermal sterilization and radiosterilization point at similar free radicals properties in the studied samples – unpaired electrons located on oxygen atoms. More free radicals, in case of used sterilization parameters, create in radiosterilized samples.
PL
Zbadano właściwości centrów paramagnetycznych upigmentowanych grzybów glebowych Cladosporium herbarum metodą EPR. Stwierdzono stabilny paramagnetyzm Cladosporium herbarum wynikający z obecności w próbce głównie eumelaniny. W widmach EPR obserwowano dominującą linię eumelaniny oraz dodatkowo linię feomelaniny o niewielkiej amplitudzie. o-Semichinonowe wolne rodniki (~10/17spin/g) odpowiadają za paramagnetyzm Cladosporium herbarum.
EN
Properties of paramagnetic centers in pigmented soil fungi Cladosporium herbarum were studied by EPR method. Stable parmagnetism of Cladosporium herbarum, mainly resulted from existence of eumelanin in the sample, was stated. Dominant line of eumelanin and additionally line of pheomelanin with the low amplitude were observed in EPR spectra. o-Semiquinone free radicals (~10/17spin/g) are mainly responsible for paramgnetism of Cladosporium herbarum.
18
Content available Badania Rhizoma calami metodą EPR
PL
Przeprowadzono badania Rhizoma calami z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego (EPR) na pasmo X (9.3 GHz). Porównano koncentrację i właściwości centrów paramagnetycznych w próbkach wyjściowych oraz sterylizowanych parą wodną. Wykazano, że wolne rodniki występują w obydwu badanych próbkach roślinnych. Ciągłe nasycenie mikrofalowe linii EPR wykazało jednorodne rozmieszczenie wolnych rodników oraz wolne procesy relaksacji spin-sieć w Rhizoma calami.
EN
Rhizoma calami was examined by electron paramagnetic resonance (EPR) spectroscopy at X-band (9.3 GHz). Concentration and properties of paramagnetic centers in the original sample and sample sterilized by water vapour were compared. It was stated that free radicals exist in both the studied plant samples. Continuous microwave saturation of EPR lines proved homogeneous distribution of free radicals and slow spin-lattice relaxation processes in Rhizoma calami.
PL
Zbadano zmiany struktury chemicznej oraz generowanie wolnych rodników w ampicylinie podczas sterylizacji w temperaturach 160 stopni C, 170 stopni C i 180 stopni C. Jako metody badawcze zastosowano spektroskopię FT-IR i EPR.. Wykazano, że sterylizacja w temperaturach od 160 stopni C do 180 stopni C powadzi do zmian struktury chemicznej ampicyliny oraz powoduje powstawanie dużej ilości wolnych rodników w próbce. Widma FT-IR uwidaczniają częściową degradację grupy karboksylowej w trakcie ogrzewania leku. Zależność kształtu widm EPR od mocy mikrofalowej wskazuje na złożony charakter układu centrów paramagnetycznych sterylizowanej ampicyliny.
EN
Changes of chemical structure and formation of free radicals in ampicyline during sterilization at temperatures 160 degrees of C, 170 degrees of C, and 180 degrees of C were studied. FT-IR and EPR were applied as experimental methods. It was proved that sterilization at temperatures from 160 degrees of C to 180 degrees of C lead to changes of chemical structure of the ampicyline and causes formation of high amount of free radicals. FT-IR spectra show that carboxyl groups are partly evolved during heating of this drug. Dependence of lineshape of EPR spectra on microwave power indicates complex character of paramagnetic centers system of ampicyline.
PL
Przeprowadzono badania właściwości paramagnetycznych biopolimeru melaninowego otrzymanego z Sepia officinalis z zastosowaniem spektroskopii elektronowego rezonansu paramagnetycznego na pasmo X (9,3 GHz). Biopolimer ten jest wykorzystywany w preparatach kosmetycznych. Analizowano kształt i parametry widm EPR centrów paramagnetycznych melaniny zarejestrowanych jako pierwsza pochodna absorpcji. Otrzymano wartości współczynnika rozszczepienia spektroskopowego g, amplitudy, intensywności integralnej i szerokości linii EPR. Wyznaczono koncentrację centrów paramagnetycznych w badanym biopolimerze melaninowym. Stwierdzono podobne widma EPR i właściwości centrów paramagnetycznych melaniny z Sepia officinalis oraz eumaleniny. Zależne od mocy mikrofalowej asymetryczne widma EPR wskazują na złożony charakter układu centrów paramagnetycznych w testowanym biopolimerze. Wykazano, że w melaninie z Sepia officinalis występują głównie o-semichinonowe wolne rodniki. Wolne procesy relaksacji spin-sieć zachodzą w analizowanej melaninie.
EN
Paramagnetic properties of melanin biopolymer from Sepia officinalis were studied by the use of electron paramagnetic resonance spectroscopy (EPR) at X-band (9.3 GHz). This biopolymer is applied in cosmetics. Lineshape and parameters of first-derivative EPR spectra of melanin paramagnetic centers were analysed. g-Factor, amplitude, integral intensity, and linewidth of EPR spectra were obtained. Concentration of paramagnetic centers in melanin biopolymer was determined. EPR spectra of melanin from Sepia officinalis and properties of its paramagnetic centers are similar to those of eumelanin. Asymmetrical EPR spectra dependent on microwave power indicate that complex paramagnetic centers system is characteristic for the tested biopolymer. It was proved that mainly o-semiquinone free radicals exist in melanin from Sepia officinalis. Slow spin-lattice relaxation processes exist in the analysed melanin.
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