Abstract We found, that dialkyl phosphite 1 and oxo-compound 2 in an equilibrium reaction give an adduct α-hydroxyphosphonate 5 un -der phase-transfer catalytic conditions [K2CO3/TEBA/dichloroethane or aromatic solvents (solid-liquid PTC); 50% NaOH/TEBA/dichloroethane or benzene (liquid-liquid PTC)]. On the other hand 3, is transformed to phosphate 4 or to α-alkoxyphosphonate 5 in the presence of alkylating agent using PTC circumstances. 相似文献
The synthesis of 3‐aryl‐2‐cyclohexenones is a topic of current interest as they are not only privileged structures in bioactive molecules, but they are also relevant feedstocks for the synthesis of substituted phenols or anilines, which are ubiquitous structural elements both in drug design and medicinal chemistry. A simple and sustainable one‐pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β‐position of cyclic ketones has been developed. Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron‐transfer mediators (ETMs) under ambient oxygen pressure. 相似文献
Mesomorphic properties and structures of two mix-substituted lipophilic phthalocyanine derivatives of the A3B type, with a different ratio of electron-donating (hexadecyloxy-) and electron-withdrawing (Cl-) substituents on the isoindol fragments ‘A’ and ‘B’, correspondingly, were studied by polarising optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. Both compounds display columnar mesophases, and the type of organisation of the columns in the mesomorphic state was found to strongly depend on the number of peripheral chlorine substituents in the molecule. The di-chloro-substituted phthalocyanine forms a solid pasty lamellar phase at room temperature, which on heating undergoes successive transitions to two large-lattice columnar mesophases (2D-Colh and 3D-MCol) arising from the aggregation of several phthalocyanine-containing piles. On the contrary, aggregation of columns does not occur for the tetra-chloro-substituted phthalocyanine, which forms a nematic columnar mesophase of single phthalocyanine piles (1D-NCol). While the di-chloro-compound partly crystallises on cooling, the nematic phase of the tetra-chloro-compound freezes at room temperature. The reasons for this different self-organisation behaviour are not yet fully understood, but some hints may be deduced from the proposed supramolecular models. 相似文献
The purpose of this study was to assess SPION’s in vitro radiosensitizer effect at 6MV-energies and to calculate nanoparticle enhancement ratio (NER) of SPIONs. Citrate coated-SPION’s were synthesized. Trypan-blue, metabolic activity tests were performed. Cell cultures were irradiated at 0,2,4,6,8 Gy at 6MV-energy. Clonogenic survival assays, NER calculations were carried out. SPIONs were biocompatible. NERs were cell-line specific and dose dependent. The highest radiosensitization were seen in radiosensitive MCF-7 and MDAH-2447 cells at 2 Gy (NER:1.49 and 1.39 respectively), in relatively radioresistant MDA-MB-231 cells at 4 Gy (NER:1.20). By increasing doses radiosensitizer effect disappeared. There is possibility that by synergistic effect, SPIONs may cause dose-dependent and cell-line specific radiosensitization at 6MV. 相似文献
A method is described for the synthesis of a nanocomposite containing FeOOH and N-doped carbon nanosheets. The nanocomposite was synthesized by a hydrothermal method using a Fe3O4/chitosan nanocomposite as the precursor. The nanocomposite displays peroxidase-like activity and catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by H2O2. This results in the formation of a blue colored product with an absorption maximum at 652 nm in the UV-vis spectra. Based on these findings, colorimetric assays were worked out for both hydrogen peroxide and glucose. The H2O2 assay works in the 5 to 19 μM concentration range, and the limit of detection is 5 nM. The glucose assay works in the 8 μM to 0.8 mM concentration range and has a 0.2 μM detection limit. The method was successfully applied to the determination of glucose in human urine.
Journal of Thermal Analysis and Calorimetry - The food-colouring dye tartrazine is a significant additive and in the same time a biologically active material. Thermal behaviour of trisodium... 相似文献
Thermal, thermomechanical, and caloric properties of commercial orthodontic wires (produced by Natural Orthodontics Corp., USA) with cylindrical and rectangular geometry were studied. Depending on the applied forces, there were identified the range of elasticity, the elasticity–viscoelasticity coexistence domain and the domain in which a maximum force of 18 N is applied, for the orthodontic wires. When increasing the thickness of orthodontic wires, deformation decreases. The Controlled Force Module, in the tension mode, was used for the determination of the orthodontic wires elongation at application of the stretching forces from 0 to 13 N, at 35 °C, maintaining each static force value for 3 min. The increase in the cross-sectional area of the orthodontic wires disfavors the process of elongation of the sample, at the same applied static force. Using the Multi-Frequency–Strain–Stress modulus, in the tension mode, DMA cyclic heating–cooling measurements were performed. The measured physical quantities for orthodontic wires were Storage Modulus, Loss Modulus, Tanδ and Stiffness, at heating and cooling. Thus, the characteristic temperatures of the phase transitions (As, Af, Ms, Mf), of all the studied orthodontic wires were identified. Also, the values of the elasticity modulus (Young’s Modulus) of the orthodontic wires were calculated at 35 °C. With the DSC Q200 device, using temperature-modulated differential scanning calorimetry method, a multi-step temperature variation program, was applied to a rectangular wire, in three stages (cooling–heating–cooling). Through the interpretation of heat fluxes (reversible, irreversible and total), the phase transitions in the formation of martensite, austenite, but also of the rombohedral phase (R-phase), were identified. Formations of austenite and martensite were also evidenced by the classical DSC method, but the classical DSC method also enabled the R-phase identification. The adherence of some food dyes on the orthodontic wires, as well as the modification of the surface roughness of the orthodontic wire after the deposition of the food dye, was also studied. By magnetic measurements, it was established that the orthodontic wires had paramagnetic properties at room temperature, and nitinol was a mixture of 49.2% austenite and 50.8% martensite.
The flaws in the Reply [1] to our paper [2] have been pointed out. Elber and Karplus (EK) have not disproved our irrefutable global statement that the energy average cannot be minimized which rebuts the theoretical background of EK-type calculations. Another statement of ours has shown that even a curve for which the average energy is locally minimal for all directional perturbations in the sense of classical variational calculus cannot be identical with the reaction path (RP) defined as a steepest descent path (SDP). EK found an error in the early preprint of our theoretical paper [3] and because of this error they qualified our correct variational statement as false for all the SDPs consisting of a straight line each. Mixing global and variational arguments, EK refuted our criticism in a logically incorrect manner. In this Comment we prove that both of our earlier statements invariably remain in force and the criticism included in those has been as well-established and solid as was before. 相似文献