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Rink C Sasse F Zubrienė A Matulis D Maier ME 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(48):14469-14478
By the replacement of an acetate with propionate by means of organic synthesis, a range of zearalenone analogues were prepared that feature an allylic methyl group. For the synthesis of the aliphatic region of the analogues, we used an asymmetric alkylation to yield pentenol derivatives 16 and ent‐ 16 . By means of hydroboration the corresponding aldehydes were secured. These were coupled with 2‐pentynol derivate 23 by means of a Carreira acetylide addition. Further routine steps led to the sulfones 29 and 45 , respectively. After merging them with 2‐bromobenzaldehyde 9 in a Julia–Kocienski reaction, metalation, carboxylation, and protecting‐group manipulations gave the seco acids 35 and 49 . By means of lactonization under Mitsunobu (alcohol activation) or Trost–Kita conditions (carboxyl activation), all four possible macrocyclic ketone stereoisomers were accessible. In all, considering various protecting‐group decorations, 16 analogues were obtained and tested for cytotoxicity (L929 mouse fibroblast cell line). Whereas most of the analogues were less active than zearalenone (IC50=9.4 μM ), the resorcinol derivatives were comparable, with one stereoisomer ( 40 b ) being slightly more active (IC50=6.6 μM ). These results were also reflected in the binding assays to Hsp90 in which 40 b showed a dissociation constant (Kd) value of 130 nM . 相似文献
24.
Donnelly RF Morrow DI McCarron PA David Woolfson A Morrissey A Juzenas P Juzeniene A Iani V McCarthy HO Moan J 《Photochemistry and photobiology》2009,85(1):195-204
Silicon microneedle (MN) arrays were used to puncture excised murine and porcine skin in vitro and transdermal and intradermal delivery of meso-tetra ( N -methyl-4-pyridyl) porphine tetra tosylate (TMP) investigated using topical application of a bioadhesive patch containing 19 mg TMP cm−2 . Animal studies, using nude mice, were then conducted to investigate the in vivo performance of the bioadhesive patch following MN puncture of skin. MN puncture significantly enhanced both intradermal and transdermal delivery of TMP in vitro , though the total amounts of drug delivered (25.22% into porcine skin and 0.07% across murine skin) were still quite small in each case. Notwithstanding this, in vivo experiments showed that MN puncture was capable of permitting a prolonged increase in TMP fluorescence at the site of application. Importantly, fluorescence was negligible at distant sites, meaning systemic delivery of the drug was not sufficient to induce TMP accumulation other than at the application site. In this study we have conclusively demonstrated proof of principle; MN puncture allows true intradermal delivery of a preformed photosensitizer in animal skin models in vitro and in vivo . Importantly, transdermal delivery was much reduced in each case. Increasing MN density would allow increased amounts of photosensitizer to be delivered. However, as MNs create aqueous pores in the stratum corneum, a preformed photosensitizer must possess at least some degree of water solubility in order to permit enhanced intradermal delivery in this way. We believe that use of MN array technology in this way has the potential to significantly improve topical photodynamic therapy of skin tumors. 相似文献
25.
This study describes a new, basic procedure for the tuning of some analytical parameters of enzymatic biosensors that are based on hydrogen peroxide-producing oxido-reductases. An amperometric biosensor based on glucose oxidase (GOx) (EC 1.1.3.4) from Penicillum vitale, immobilized on a carbon rod electrode by cross-linking with glutaraldehyde, was exploited as a model system for demonstration of the approach described here. Such an important analytical parameter as the upper detection limit was dramatically changed by the formation of a polypyrrole conducting polymer layer by the GOx-induced polymerization of polypyrrole (Ppy). An increase in the upper detection limits for differently modified electrodes was estimated by calculation of the apparent Michaelis-Menten constant [K(M(app))]. A significant increase in the long-term stability of the GOx-based electrode modified by Ppy (GOx/Ppy) was detected compared with that of an unmodified one. Further application of this approach, based on the self-encapsulation of glucose oxidase and other oxidases, is predicted for such biosensors where extension of the detection rate as well as K(M(app)) are required. 相似文献
26.
Almira Ramanaviciene Asta Kausaite-Minkstimiene Yasemin Oztekin Geta Carac Jaroslav Voronovic Natalija German Arunas Ramanavicius 《Mikrochimica acta》2011,175(1-2):79-86
We describe a new method for the visualization of the activity of red-ox proteins on a gold interface. Glucose oxidase was selected as a model system. Surfaces were modified by adhesion of glucose oxidase on (a) electrochemically cleaned gold; (b) gold films modified with gold nanoparticles, (c) a gold surface modified with self-assembled monolayer, and (d) covalent immobilization of protein on the gold surface modified with a self-assembled monolayer. The simple optical method for the visualization of enzyme on the surfaces is based on the enzymatic formation of polypyrrole. The activity of the enzyme was quantified via enzymatic formation of polypyrrole, which was detected and investigated by quartz microbalance and amperometric techniques. The experimental data suggest that the enzymatic formation of the polymer may serve as a method to indicate the adhesion of active redox enzyme on such surfaces. Figure
An optical method for the evaluation of activity and distribution of glucose oxidase on the different surfaces was described. The enzymatic synthesis of polypyrrole (black colour) was successfully applied for the visualization of active enzyme on the surfaces. 相似文献
27.
Asta Orentien? Vilma Ol?auskait? Vida Vi?ka?kait? Audrius Padarauskas 《Chromatographia》2011,73(1-2):17-24
Ultra-performance liquid chromatography (UPLC) in reversed-phase (RP), ion pair (IP) and hydrophilic interaction chromatography (HILIC) has been investigated for the separation of imidazolium-based ionic liquid (IL) cations. Among the three stationary phases (i.e., C18, C8 and phenyl) studied under RP conditions the phenyl phase provided much stronger retention for the IL cations. Four acids (hydrochloric, methanesulfonic, perchloric and trifluoroacetic) as mobile phase additives were compared in light of their effects on the retention of IL cations. It was shown that the retention of all IL cations decreased upon acidification of the mobile phase, possibly due to suppression of residual silanol ionization. Very fast (~3 min) and efficient RP-UPLC separation of six cations was achieved by gradient elution with acetonitrile?Cwater mobile phase containing 2.5 mmol L?1 perchloric acid. In IP-UPLC all solutes were well resolved in about 4 min by gradient elution with acetonitrile?Cwater mobile phase containing 1 mmol L?1 sodium 1-octanesulfonate as ion pairing reagent. Finally, under HILIC conditions by using isocratic elution with acetonitrile?Cwater (85:15, v/v) mobile phase containing 5 mmol L?1 ammonium formate (pH 3.2) the separation time was reduced to less than 2 min while maintaining excellent peak shapes and sufficient resolution. Compared to current LC systems UPLC allowed considerably faster separations with better peak shapes. 相似文献
28.
Rasa Garjonyte Jurga Budiene Linas Labanauskas Asta Judzentiene 《Molecules (Basel, Switzerland)》2022,27(13)
Leaves and stems of red raspberry (Rubus idaeus) are used in Lithuanian folk medicine. Healing properties of raspberry are related to the content of bioactive compounds, mainly polyphenols. Extracts of raspberry leaves contained higher total phenolic content (TPC) (1290 mg/L, expressed in gallic acid equivalent) compared to that in extracts of stems or peeled bark (up to 420 mg/L and 598 mg/L, respectively). To find out whether the collection time of herbal material was critical for the properties of the extracts, the stems were collected at different times of the year. TPC in the extracts depended more on extraction conditions rather than on the sampling time. Antioxidant activity of raspberry stem and bark extracts tested by spectrophotometric (DPPH● scavenging) and electrochemical (cyclic and differential pulse voltammetry) assays correlated with TPC. DPPH radical scavenging activity values for stem, leaf, and bark extracts were as follows: ≤1.18 ± 0.07, 1.63 ± 0.10, and ≤1.90 ± 0.04 (mmol/L, TROLOX equivalent), respectively. Assessed electrochemically, hydrogen peroxide-scavenging activity of extracts was independent on TPC. The latter activity was related to the presence of some protein in the extract as revealed by gel electrophoresis. Prooxidant activity of raspberry stem extracts was dependent on solution pH and temperature. 相似文献
29.
Karolina Dzedulionyt Melita Veikait Vít Morvek Vida Malinauskien Greta Ra
kauskien Algirdas a
kus Asta
ukauskait Egl Arba
iauskien 《Molecules (Basel, Switzerland)》2022,27(24)
A general approach towards the synthesis of tetrahydro-4H-pyrazolo[1,5-a][1,4]diazepin-4-one, tetrahydro[1,4]diazepino[1,2-a]indol-1-one and tetrahydro-1H-benzo[4,5]imidazo[1,2-a][1,4]diazepin-1-one derivatives was introduced. A regioselective strategy was developed for synthesizing ethyl 1-(oxiran-2-ylmethyl)-1H-pyrazole-5-carboxylates from easily accessible 3(5)-aryl- or methyl-1H-pyrazole-5(3)-carboxylates. Obtained intermediates were further treated with amines resulting in oxirane ring-opening and direct cyclisation—yielding target pyrazolo[1,5-a][1,4]diazepin-4-ones. A straightforward two-step synthetic approach was applied to expand the current study and successfully functionalize ethyl 1H-indole- and ethyl 1H-benzo[d]imidazole-2-carboxylates. The structures of fused heterocyclic compounds were confirmed by 1H, 13C, and 15N-NMR spectroscopy and HRMS investigation. 相似文献
30.
We investigate the effect of temperature on the structure and shear response of a Σ11 asymmetric tilt grain boundary in a classical embedded-atom model of elemental copper using molecular dynamics simulations. As the temperature is increased the structure of the boundary disorders considerably, but with a boundary width that remains finite at the melting point. The disordering of the boundary structure becomes significant for homologous temperatures above 0.83 (1100?K). As temperature increases above this point the boundary width and roughness increases monotonically. Near the temperature where the boundary starts to disorder we observe a change in the temperature dependence of the ideal shear strength of the boundary, as well as the value of the coupling parameter β, defined as the ratio of the velocity of relative translation of the grains parallel to the boundary plane to that corresponding to the motion of the boundary normal to its plane. 相似文献