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111.
This paper describes the fabrication of graphene on glassy carbon electrode (GCE) by electrochemical reduction of graphene oxide (GO) attached through 1,6-hexadiamine on GCE and the simultaneous determination of structurally similar four purine derivatives using the resultant electrochemically reduced GO (ERGO) modified electrode. The electrocatalytic activity of ERGO was investigated toward the oxidation of four important purine derivatives, uric acid (UA), xanthine (XN), hypoxanthine (HXN) and caffeine (CAF) at physiological pH. The modified electrode not only enhanced the oxidation currents of the four purine derivatives but also shifted their oxidation potentials toward less positive potentials in contrast to bare GCE. Further, it successfully separates the voltammetric signals of the four purine derivatives in a mixture and hence used for the simultaneous determination of them. Selective determination of one purine derivative in the presence of low concentrations other three purine derivatives was also realized at the present modified electrode. Using differential pulse voltammetry, detection limits of 8.8 × 10−8 M, 1.1 × 10−7 M, 3.2 × 10−7 M and 4.3 × 10−7 M were obtained for UA, XN, HXN and CAF, respectively. The practical application of the modified electrode was demonstrated by simultaneously determining the concentrations of UA, XN, HXN and CAF in human blood plasma and urine samples. 相似文献
112.
Preparation of nanosized crystalline TiO2 particles at low temperature for photocatalysis 总被引:1,自引:0,他引:1
Nanocrystalline titanium dioxide (TiO2) particles were prepared by a modified alkoxide method under acidic conditions at temperatures ranging from 60°C to 90°C. The reaction temperature was used to control the crystalline phase of the TiO2 particles. At 60°C and 75°C rutile was formed whilst at 90°C anatase and brookite were formed.The photocatalytic activity of the prepared particles was tested for the degradation of sucrose. The photocatalytic activities of the prepared nanosized TiO2 were compared to those obtained from Degussa P-25 TiO2 as well as TiO2 crystalline samples prepared using the conventional sol–gel/heat treatment method. At low organic concentrations, Degussa P-25 exhibited higher photocatalytic behaviour than all the prepared particles while, at high organic concentrations, the nanosized TiO2 particles prepared at low temperature displayed an activity comparable to Degussa P-25 but much higher than the heat treated sample. The formation of excess intermediates during the degradation of higher sucrose loadings is believed to hinder the photoactivity of Degussa P-25, while the prepared TiO2 particles are able to maintain their activity for the degradation of the intermediates of sucrose. 相似文献
113.
A new naturally occurring ent-kaurane diterpenoid dimer, 15β, 15′β-oxybis (ent-kaur-16-en-19-oic acid) (1) along with six known compounds, 15β-hydroxy-ent-kaur-16-en-19-oic acid (2), 15β-hydroxy-ent-kaur-16-en-19-oate-β-d-glucopyranoside (3), 6-hydroxykaempferol-3, 7-dimethyl ether (4), quercetagetin 3, 7, 3′-trimethyl ether (5), β-sitosterol (6) and β-sitosterol glucoside (daucosterol) (7) were isolated from the aerial parts of Pulicaria inuloides DC. Compounds 2–5 were isolated for the first time from genus Pulicaria. The structures of compounds 1–7 were established on the basis of extensive 1D and 2D NMR spectroscopic techniques in combination with ESI-MS. The antimicrobial activity of the isolated compounds was evaluated against Staphylococcus aureus, Escherichia coli and Candida albicans. Sulphorhodamine B cytotoxic assay against HepG2 (liver cancer) cell line and ABTS antioxidant assay were carried out. 相似文献
114.
This study evaluated nine stripping PSA cycle configurations, all with a heavy reflux (HR) step, some with a light reflux
(LR) step, and some with a recovery (REC) or feed plus recycle (F+R) step, for concentrating CO2 from stack and flue gas at high temperature (575 K) using a K-promoted HTlc. Under the process conditions studied, the addition
of the LR step always resulted in a better process performance; and in all cases, the addition of a REC or F+R step surprisingly
did not affect the process performance except at low feed throughputs, where either cycle step resulted in a similar diminished
performance. The best cycle based on overall performance was a 5-bed 5-step stripping PSA cycle with LR and HR from countercurrent
depressurization (CnD) (98.7% CO2 purity, 98.7% CO2 recovery and 5.8 L STP/hr/kg feed throughput). The next best cycle was a 5-bed 5-step stripping PSA cycle with LR and HR
from LR purge (96.5% CO2 purity, 71.1% CO2 recovery and 57.6 L STP/hr/kg feed throughput). These improved performances were caused mainly by the use of a very small
purge to feed ratio (γ=0.02) for the former cycle and a larger one (γ=0.50) for the latter cycle. The former cycle was good for producing CO2 at high purities and recoveries but at lower feed throughputs, and the latter cycle was useful for obtaining CO2 at high purities and feed throughputs but at lower recoveries. The best performance of a 4-bed 4-step stripping PSA cycle
with HR from CnD was disappointing because of low CO2 recoveries (99.2% CO2 purity, 15.2% CO2 recovery and 72.0 L STP/hr/kg feed throughput). This last result revealed that the recoveries of this cycle would always
be much lower than the corresponding cycles with a LR step, no matter the process conditions, and that the LR step was very
important to the performance of these HR cycles for this application and process conditions studied. 相似文献
115.
116.
Bidentate phosphine ligands have been prepared on polystyrene beads modified with polyether dendron spacers. When complexed to Pd(0), these systems exhibited a negative dendritic effect on Heck catalysis (contrary to the analogous monodentate phosphine systems), but mostly a positive influence on carbonylation. This opposite influence of the dendronization falls into line with other differences in the optimal ligand structure for the two reactions. The negative effect on the Heck catalysis with bidentate phosphines may indicate that dendrimer-induced reduction in the cross-linking upon Pd complexation is responsible for the positive effect in the corresponding monodentate phosphine systems. 相似文献
117.
Dr. Quentin Le Dé Dr. Amal Bouammali Dr. Christian Bijani Dr. Laure Vendier Dr. Iker del Rosal Dr. Dmitry A. Valyaev Dr. Chiara Dinoi Dr. Antoine Simonneau 《Angewandte Chemie (International ed. in English)》2023,62(40):e202305235
We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] ( 1 , Cp=η5-cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li ( 3 ) that is stable only below −40 °C. Full characterization of 3 (including single crystal X-ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li ( 2 ). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so-far unique behavior of the N2 ligand in 1 . DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal-coordinated N2 remains to be demonstrated. 相似文献
118.
This work aims at studying the optimization of an on‐line capillary electrophoresis (CE)‐based tryptic digestion methodology for the analysis of therapeutic polypeptides (PP). With this methodology, a mixture of surrogate peptide fragments and amino acid were produced on‐line by trypsin cleavage (enzymatic digestion) and subsequently analyzed using the same capillary. The resulting automation of all steps such as injection, mixing, incubation, separation and detection minimizes the possible errors and saves experimental time. In this paper, we first study the differents parameters influencing PP cleavage inside the capillary (plug length, reactant concentration, incubation time, diffusion and electrophoretic plugs mixing). In a second part, the optimization of the electrophoretic separation conditions of generated hydrolysis products (nature, pH and ionic strength (I) of the background electrolyte (BGE)) is described. Using the optimized conditions, excellent repeatability was obtained in terms of separation (migration times) and proteolysis (number of products from enzymatic hydrolysis and corresponding amounts) demonstrating the robustness of the proposed methodology. 相似文献
119.
Reactivity of N,N″‐1,ω‐alkanediyl‐bis‐[N′‐organylthiourea] Derivatives Towards Isatylidene Malononitrile 下载免费PDF全文
Alaa A. Hassan Kamal M. A. El‐Shaieb Amal S. Abd El‐Aal Stefan Bräse Martin Nieger 《Journal of heterocyclic chemistry》2016,53(6):2025-2029
(Z)‐2‐(2‐Oxoindolin‐3‐ylidene)‐2‐(substituted amino)acetonitriles, 2‐thioxoimidazolidine‐1‐carbothioamides, and 2‐thioxotetrahydropyrimidine‐1(2H)‐carbothioamides were synthesized via conventional thermal or microwave‐assisted reaction of isatylidene malononitrile with N,N″‐1,ω‐alkanediyl‐bis‐[N′‐organylthiourea] derivatives. Rationale for these conversations involving the nucleophilic addition on the dicyanomethylene carbon atom and intramolecular heterocyclization of the title compounds is presented. The structure of the (Z)‐2‐(2‐oxoindolin‐3‐ylidene)‐2‐(phenylamino)acetonitrile has been confirmed by the X‐ray analysis. 相似文献
120.
Ashraf N. Abdalla Waleed H. Malki Amal Qattan Imran Shahid Mohammad Akbar Hossain Muhammad Ahmed 《Molecules (Basel, Switzerland)》2021,26(2)
Colorectal cancer (CRC) remains one of the main causes of death worldwide and in Saudi Arabia. The toxicity and the development of resistance against 5 fluorouracil 5FU pose increasing therapeutic difficulties, which necessitates the development of personalized drugs and drug combinations. Objectives: First, to determine the most important kinases and kinase pathways, and the amount of ABC transporters and KRAS in samples taken from Saudi CRC patients. Second, to investigate the chemosensitizing effect of LY294002 and HAA2020 and their combinations with 5FU on HT29, HT29-5FU, HCT116, and HCT116-5FU CRC cells, their effect on the three ABC transporters, cell cycle, and apoptosis, in light of the important kinase pathways resulting from the first part of this study. Methods: The PamChip® peptide micro-array profiling was used to determine the level of kinase and targets in the Saudi CRC samples. Next, RT-PCR, MTT cytotoxicity, Western blotting, perturbation of cell cycle, annexin V, and immunofluorescence assays were used to investigate the effect on CRC, MRC5, and HUVEC cells. Results: The kinase activity profiling highlighted the importance of the PI3K/AKT, MAPK, and the growth factors pathways in the Saudi CRC samples. PIK3CA was the most overexpressed, and it was associated with increased level of mutated KRAS and the three ABC transporters, especially ABCC1 in the Saudi samples. Next, combining HAA2020 with 5FU exhibited the best synergistic and resistance-reversal effect in the four CRC cells, and the highest selectivity indices compared to MRC5 and HUVEC normal cells. Additionally, HAA2020 with 5FU exerted significant inhibition of ABCC1 in the four CRC cells, and inhibition of PIK3CA/AKT/MAPK7/ERK in HT29 and HT29-5FU cells. The combination also inhibited EGFR, increased the preG1/S cell cycle phases, apoptosis, and caspase 8 in HT29 cells, while it increased the G1 phase, p21/p27, and apoptosis in HT29-5FU cells. Conclusion: We have combined the PamChip kinase profiling of Saudi CRC samples with in vitro drug combination studies in four CRC cells, highlighting the importance of targeting PIK3CA and ABCC1 for Saudi CRC patients, especially given that the overexpression of PIK3CA mutations was previously linked with the lack of activity for the anti-EGFRs as first line treatment for CRC patients. The combination of HAA2020 and 5FU has selectively sensitized the four CRC cells to 5FU and could be further studied. 相似文献