Photooxidation of acyclovir with thermally generated triplet excited ketones. A comparison with type I and II photosensitizers

The antiviral drug acyclovir (Ac, 1) was treated with triplet excited ketones, which have been generated in thermal decomposition of 3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane (HTMD), in the dark. Three major oxidation products were detected by means of spectroscopic measurements. The products were (2-hydroxyethoxy) methyl spiroiminodihydantoin (2), (2-hydroxyethoxy) methyl (amino)-2-imino-1,2-dihydroimidazole-5-one (3), and 2,2-diamino-4-[(2-hydroxyethoxy) methyl) amino)-5-[2H]-oxazolone (4). Equal amounts of type I and type II photooxidation products were found, as could be established by comparison with predominant type I (riboflavin) and type II (rose bengal) photosensitizers. The concentration and time profiles for the HTMD-induced oxidation of Ac were also determined. The participation of singlet oxygen in HTMD-induced oxidation was confirmed by the substantial D(2)O effect in the formation of spiroiminodihydantoin (2).     

A study of the silver form of a natural zeolitic material of the clinoptilolite type

The silver forms of a natural zeolitic material (from the East Slovakian deposit) on the clinoptilolite type has been prepared. The silver forms of the natural zeolitic material were investigated by X-ray powder diffractometry, IR spectroscopy, ESCA measurements, scanning electron microscopy and conductivity measurements. Depending on the preparation conditions, the content of silver ions in the zeolitic products was found to be in the range from 16 to 24%. In the sample with a silver loading of 18.6%, the silver uptake is due to an ion exchange process, mostly involving Na(I), Ca(II) and Mg(II) ions.     

Tetracyano complexes incorporated in natural zeolitic materials

New compounds, possibly of the host-guest type, were prepared by the combination of a natural zeolitic material of the clinoptilolite type and Ni(NH₃)₂Ni(CN)₄·2.75 H₂O. The new compounds showed an increase of crystallinity in the diffractographic measurements. The measured IR spectra, thermal analysis and GC experiments were used to identify the products.     

几种尖晶石型复合氧化物纳米粉体的制备及气敏性

采用化学共沉淀法合成了4种尖晶石型复合氧化物MFe₂O₄(M=Cu²⁺,Zn²⁺,Cd²⁺,Mg²⁺).X射线粉末衍射分析、透射电镜及比表面测定等表征结果表明它们均为具有较大比表面积的纳米粉体,平均粒径<50nm.将样品做成厚膜型气敏元件,测定了其对乙炔、液化石油气、一氧化碳、氢气和乙醇等还原(可燃)性气体的气敏特性。     

Core-shell type polymer microspheres prepared by domain fixing of block copolymer films

Well-defined poly[styrene(S)-b-isoprene(I)] diblock copolymers were prepared by sequential anionic addition. The crosslinking reactions of polyisoprene (PI) spherical domains of these block copolymers were carried out in a n-hexane solution of sulfur monochloride (S₂Cl₂). Electron micrograph of crosslinked products indicates the structure of core-shell type polymer microspheres. It is found from NMR and turbi+imetric measurements that the solubility of core-shell type polymer microspheres depends strongly on that of block chains comprising the shell portion. The particle size of these microspheres shows a narrow distribution.     

Identification of the oxidation products of the reaction between alpha-pinene and hydroxyl radicals by gas and high-performance liquid chromatography with mass spectrometric detection

In this paper an identification method is described for determining the degradation products of the reaction of alpha-pinene with hydroxyl radicals. The study is carried out in a fast-flow reactor equipped with a specially designed microwave cavity (type Surfatron) allowing to operate at pressures up to 100 Torr (1 Torr=133.322 Pa). The semivolatile products are collected on a liquid nitrogen trap (LN2 trap) and the batch samples are subsequently analysed by GC-MS and HPLC-MS. Some samples were also collected directly on a LpDNPH-cartridge, followed by HPLC-MS analysis. When experiments were carried out at 50 Torr both GC-MS and HPLC-MS measurements showed that campholenealdehyde and pinonaldehyde were identified as condensable oxidation products for the alpha-pinene/OH reaction, with pinonaldehyde being the main product. Furthermore, the LN2 trap collection method based on the in situ conversion of aldehydes and ketones to their 2,4-dinitrophenylhydrazone derivatives allowed the determination of formaldehyde, acetaldehyde and acetone. Although formaldehyde and acetone are present in small amounts in blank samples it could be established that formaldehyde and acetone are also formed in the alpha-pinene/OH reaction.     

Radon concentrations and absorbed dose measurements in a Pleistocenic cave

Radon concentration measurements were carried out using solid-state nuclear track-etch detectors (SSNTDs) type CA 80-15 cellulose nitrate films, in a Pleistocenic cave at Petralona, in Halkidiki, Northern Greece, at 55 km from the city of Thessaloniki. Radon levels as high as 88 kBq^.m^-3 (2.38 nCi^.l^-1) have been recorded inside the cave equivalent to 11.90 WL in terms of occupational exposure to radon and its decay products. Absorbed dose rates were performed using TL dosimeters, type TLD-200 (CaF₂-Dy) in a continuous monitoring program (integrated measurements). Dose rate levels as high as 110 nGy^.h^-1 were recorded inside the cave. In interpreting the high levels of radiation doses, radioactivity measurements regarding the naturally occurring ²³⁸U, ²³²Th and ⁴⁰K radionuclides were carried out in various speleothems found at different sites in the cave.     

Thiophene-thiophene versus phenyl-phenyl coupling in 2-(Diphenylamino)-Thiophenes: an ESR-UV/Vis/NIR spectroelectrochemical study.

The oxidation of several 2-diphenylamino-substituted thiophenes and N,N'-bis(2-diphenylamino-5-thienyl)-substituted phenylene-1,4-diamines with different substitution patterns in the 5-position of their thiophene moieties was studied by cyclovoltammetric and spectroelectrochemical measurements (ESR, UV/Vis/NIR). These measurements revealed both the structure of the oxidation products obtained and that of their cationic intermediates, as well as the pathway of their formation and follow-up reactions. Thus, the formation of the radical cations in the first electrochemical oxidation step of the target molecules was demonstrated. Depending on the substitution pattern, these radical cations give rise to several consecutive processes to a different extent. Thus radical dimers, dehydrodimers with a 2,2-bithiophene, 3,3'-bithiophene, or benzidine structure, as well as radical monocationic and dicationic products can be formed. For N,N'-bis(2-diphenylamino-5-thienyl)-substituted phenylene-1,4-diamines rather stable radical cations and dications were primarily formed and unambiguously identified. These species were transformed into 2,2'-bithiophene dimers and oligomers when the 5-position of the thiophene moiety was unsubstituted. By in situ spectroelectrochemistry the influence of the substituents on the type of coupling reactions can be demonstrated and followed in detail.     

Decomposition of 2-propanol on an intermetallic compound for hydrogen storage

Decompositon of 2-propanol has been carried out on the hydrogen storage material Mg₂Cu and its modified form (OH–Mg₂Cu) to study their catalytic behavior. The reaction was carried out in a continuous flow type reactor in the temperature range of 403–513 K at various flow rates. Mg₂Cu showed good catalytic activity with large amounts of condensation products. Its modified form gave acetone as the only products. The reason for these differences is explained in terms of differences in the structure of the catalyst as determined by XRD and XPS, as well as by surface area measurements. The reason for the formation of condensation products is discussed.     

Dialkenylgermanes as Precursors of Silsesquioxane‐based Macromolecular Structures

Herein we report a study of highly efficient platinum‐catalyzed hydrosilylation of dialkenylgermanes with silsesquioxanes and spherosilicates. The use of divinyl‐ and diallylgermanes allowed the synthesis of new classes of compounds, i. e., dumbbell‐type systems, silsesquioxanes with alkenyl pendant group, and oligomeric derivatives. The results are supported by detailed data from in situ FT‐IR and NMR measurements, enabling precise monitoring of the reaction progress and determination of regioselectivity of the formed products.     

肉类制品中微量锶的分离及^87Sr/^86Sr同位素比值测定

利用87Sr/86Sr同位素比值进行生物和古人类源区与迁徙的示踪是Sr同位素技术应用的新领域,也是考古研究和肉类食品溯源研究的新尝试。本研究对牛肉干粉采用酸溶、微波消解和灰化后硝酸提取等不同方法进行消解,比较了它们的离子交换分离效果和Sr同位素测定结果;用石英、石墨和瓷坩埚3种器皿对牛肉干粉进行灰化,检测了灰化器皿对87Sr/86Sr同位素比值的影响,从而确定了石英坩埚灰化的消解方法,建立了适合于肉类制品微量Sr的化学分离方法与87Sr/86Sr同位素比值测定方法。本方法包括肉类制品的石英坩埚灰化、离子交换分离和87Sr/86Sr比值的热离子化质谱测定。所建方法对肉类食品溯源和考古研究等领域富含有机质样品的Sr同位素比值测定具有普适性。     

Radiation induced degradation of ketoprofen in dilute aqueous solution

The intermediates and final products of ketoprofen degradation were investigated in 0.4 mmol dm^?3 solution by pulse radiolysis and gamma radiolysis. For observation of final products UV?vis spectrophotometry and HPLC separation with diode array detection were used, and for identification MS was used. The reactions of ^?OH lead to hydroxycyclohexadienyl type radical intermediates, in their further reactions hydroxylated derivatives of ketoprofen form as final products. The hydrated electron is scavenged by the carbonyl oxygen and the electron adduct protonates to ketyl radical ^?OH is more effective in decomposing ketoprofen than hydrated electron. Chemical oxygen demand and total organic carbon content measurements on irradiated aerated solutions showed that using irradiation technology ketoprofen can be mineralised. The initial toxicity of the solution monitored by the Daphnia magna test steadily decreases with irradiation. Using 5 kGy dose no toxicity of the solution was detected with this test.     

Determination of the oxidation products of the reaction between alpha-pinene and hydroxyl radicals by high-performance liquid chromatography

In this paper a method is described for determining and quantifying the degradation products of the reaction of alpha-pinene with hydroxyl radicals. The study is carried out in a fast-flow reactor equipped with a specially designed microwave cavity (type Surfatron) allowing to operate at pressures up to 100 Torr (1 Torr=133.322 Pa). The semi-volatile products are collected on a liquid nitrogen trap (LN2 trap) coated with a 2,4-dinitrophenylhydrazine (2,4-DNPH) solution and the batch samples are subsequently analyzed by HPLC. In order to perform quantitative measurements the batch samples contained two internal standards: benzaldehyde-2,4-DNPH and tolualdehyde-2,4-DNPH. In the experiments carried out at 50 Torr and 100 Torr, HPLC measurements showed that the semi-volatile products formaldehyde, acetaldehyde, acetone, campholenealdehyde and pinonaldehyde could be quantified as oxidation products for the alpha-pinene/OH reaction, with pinonaldehyde being the main product. Assuming that all these five oxidation products have the same collection efficiency on the LN2 trap, one arrives at the following relative product yields (expressed in mol %) at 50 and 100 Torr, respectively: 9.7+/-0.7 and 6+/-5 for formaldehyde; 1.1+/-0.1 and 0.9+/-0.5 for acetaldehyde; 16+/-1 and 6+/-2 for acetone; 11+/-2 and 5.5+/-0.7 for campholenealdehyde; 63+/-3 and 82+/-7 for pinonaldehyde.     

Mechanism of action of pyrogenic silica as a smoke suppressant for polystyrene

The kinetic laws governing the forced burning of polystyrene-pyrogenic silica composites suggested formation of a surface “skin”; direct thermomechanical measurements were subsequently made of rates and extents of skin formation as a function of the type and loading of silica present; investigations were carried out on the effects of composition of the surrounding atmosphere, heating rate and degree of physical contact between the polymer and the additive on the amount of carbonaceous residue formed during thermal decomposition of the polymeric composites; and measurements were made of the influence of oxygen concentration on the extent of fuel retention when the composites burn. Silanol groups on the surface of the silica appear to react chemically with free radical species formed during the oxidative breakdown of polystyrene; this interaction results in the production of a skin, consisting of a cross-linked polymer structure with silica particles embedded in it and preventing the escape of the volatile decomposition products of the polymer which would otherwise lead to smoke formation. A parameter has been defined, the adsorption capacity, which is of crucial importance in the control of smoke generation, and a model has been devised which accounts for many of the experimental correlations found.     

Fast sensitive analysis of uranium and thorium in natural samples based on delayed neutron counting using an ultrafast conveyor tube system

A fast, sensitive and routine methode for quantitative analysis of uranium and thorium in natural samples is described. The identification is done by counting the delayed neutrons of mainly the short living fission products after sample-irradiation with and without cadmium shielding. The rabbit system used is installed at the Forschungsreaktor Neuherberg, type TRIGA Mark III. The limits of detection (relative to 2 g of sample weight) were specified to be 20 ppb (U) and 3 ppm (Th) using puls irradiations, 150 ppb (U) and 15 ppm (Th) using 1 MW steady state reactor power. A single determination is done within less than 60 s. The methods were proved by about 3000 measurements also including comparison experiments.     

Formation and properties of hydrophobic CeO2 nanoparticles

Uniform hydrophobic cerium oxide (CeO₂) nanoparticles in a cubic structure with an average size of 4.6 nm were obtained by a novel oil-water interface method in the presence of 0.40 M NaOH. Effects of reactants concentration, oxidation reaction temperature, and the type of surfactants on the final products were investigated. The products were characterized by X-ray diffraction, transmission electron microscopy, UV-visible spectroscopy, room-temperature photoluminescence spectroscopy and contact angle measurements. The products exhibited high luminescence and strong hydrophobicity. The data suggest that Ce(OH) _x ^4?x (x < 4) is a precursor complex for the formation of CeO₂ nanoparticles in liquid phase and its concentration controls the size of CeO₂ particles. The adsorption of the surfactant influences the formation of the hydrophobic particles of CeO₂ by the oil-water interface method.     

Reaction of substituted furan-2-carboxaldehydes and furo[b]pyrrole type aldehydes with hippuric acid

4-Heteroarylidene-2-phenyl-1,3-oxazol-5(4H)-ones were prepared by reactions of hippuric acid with substituted furan-2-carboxaldehydes or furo[b]pyrrole type aldehydes. The reactivity of various furan-2-carboxaldehyde derivatives in this reaction is discussed. The effect of microwave irradiation on some condensation reactions was compared with "classical" conditions. The results show that microwave irradiation shortens the reaction times while affording comparable yields. Elementary analysis, UV, IR and 1D NMR proved the structure of new synthesised compounds. 2D NMR spectroscopic measurements confirmed that the configuration at the carbon-carbon double bond corresponds to the pure E isomers of the products.     

Differential thermal analysis and heat flow calorimetry of coffee and chicory products

The techniques of differential thermal analysis (DTA) and heat flow calorimetry were used to study the thermal behaviour of coffee and chicory products above 20°C. Intensive exothermic reactions were particularly evident when measurements were made under pressure, which prevents vaporization of the water contained in the products, in the temperature domain of interest.     

制备方法对LaFeO3纳米粉体的影响

分别采用熔盐法和溶液燃烧法合成了钙钛矿型LaFeO3纳米粉体,系统研究了两种制备方法对粉体相结构、形貌的影响,用XRD、SEM和TG/DSC对纳米粉体进行了表征.结果表明:熔盐体系、煅烧温度、燃料类型和燃料/氧化剂的摩尔比对合成LaFeO3有重要的影响.450-750℃的熔盐NaNO2体系及650-800℃的熔盐NaN...     

Thermal decomposition of organic peroxide with metals using calorimeters

In this study, we evaluated the reactivity of organic peroxides with metals. The effect of the metals on the decomposition of organic peroxides was measured using a differential scanning calorimeter (DSC). Results of DSC measurements showed that some organic peroxides have high reactivity with a gold plated cell. Especially, hydroperoxides were decomposed at lower temperature using the gold plated cell when compared to other type of cells. In order to evaluate the effect of metals on the hydroperoxides, the decomposition characteristics of cumenhydroperoxide (CHP) with metal powders were studied using a C80 calorimeter and the products were analyzed by a gas chromatograph. These results indicated that the radical reaction of CHP was catalyzed by the gold and the autocatalytic reaction of CHP was catalyzed by stainless steel (SUS) and hastelloy c (HC).