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41.
Yosselin Huentupil Patricio Chung Néstor Novoa A. Hugo Klahn Manuela E. Medina Jonathan Cisterna Iván Brito Andrés Rivera Rodrigo López-Muñoz Rodrigo Arancibia 《应用有机金属化学》2020,34(9):e5788
In the research of new compounds with multifunctional applications, heterobinuclear palladium (II) complexes based on organometallic dithiocarbazates (DTCZs) have been isolated. The organometallic DTCZ ligands of the general formula [{(η5-C5H4)-CH=NNHC(S)SCH3}]MLn [MLn = Re (CO)3 ( 2a ); Mn (CO)3 ( 2b ); FeCp ( 2c )] were prepared by the reaction between formyl organometallic precursors ( 1a−c ) with S-methyldithiocarbazate. Subsequently, a two-step reaction of 2a−c with: (i) K2[PdCl4] and (ii) PPh3 yielded heterobinuclear complexes [Pd{MLn(η5-C5H4)-CH=NNHC(S)SCH3}–(Cl)(PPh3)] [MLn = Re (CO)3 ( 3a ); Mn (CO)3 ( 3b ); FeCp ( 3c )]. All compounds were characterized by conventional spectroscopic techniques (infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis). In addition, the molecular structures of 2a , 2c and 3c were determined by single-crystal X-ray diffraction. The new palladium (II) complexes ( 3a−c ) were evaluated as antiproliferative agents against non-small cell lung cancer cells (H1299 cells). Complexes 3a and 3b containing cyrhetrenyl- and cymantrenyl-DTCZ ligands, respectively, were more active than their ferrocenyl analogue 3c . The activity was associated with the electron-withdrawing properties of the (η5-C5H4)M (CO)3 moieties and their better lipophilicity than that of the ferrocenyl analogue. In addition, we studied the capacity of metalloligands ( 2a−c ) and palladium (II) complexes ( 3a−c ) to remove methylene blue in water under UV–visible light irradiation. The results established that the complexes showed moderate efficiency and were less active than their corresponding free ligands. 相似文献
42.
Karen Beatriz Méndez-Rodríguez Nicté Figueroa-Vega César Arturo Ilizaliturri-Hernandez Mónica Cardona-Alvarado Jaime Antonio Borjas-García Carlos Kornhauser Juan Manuel Malacara Rogelio Flores-Ramírez Francisco Javier Pérez-Vázquez 《Biomedical chromatography : BMC》2020,34(12):e4956
Metabolomics is a potential tool for the discovery of new biomarkers in the early diagnosis of diseases. An ultra-fast gas chromatography system equipped to an electronic nose detector (FGC eNose) was used to identify the metabolomic profile of Volatile Organic Compounds (VOCs) in type 2 diabetes (T2D) urine from Mexican population. A cross-sectional, comparative, and clinical study with translational approach was performed. We recruited twenty T2D patients and twenty-one healthy subjects. Urine samples were taken and analyzed by FGC eNose. Eighty-eight compounds were identified through Kovats's indexes. A natural variation of 30% between the metabolites, expressed by study groups, was observed in Principal Component 1 and 2 with a significant difference (p < 0.001). The model, performed through a Canonical Analysis of Principal coordinated (CAP), allowed a correct classification of 84.6% between healthy and T2D patients, with a 15.4% error. The metabolites 2-propenal, 2-propanol, butane- 2,3-dione and 2-methylpropanal, were increased in patients with T2D, and they were strongly correlated with discrimination between clinically healthy people and T2D patients. This study identified metabolites in urine through FGC eNose that can be used as biomarkers in the identification of T2D patients. However, more studies are needed for its implementation in clinical practice. 相似文献
43.
44.
Dr. Peiyu Ge Dr. Mohamad Hojeij Dr. Micheál D. Scanlon Prof. Hubert H. Girault 《Chemphyschem》2020,21(24):2630-2633
H2 may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H2 production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc+) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc+ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc+ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO2 (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc+ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger. 相似文献
45.
Lennon Ó Náraigh 《The Journal of mathematical sociology》2020,44(1):42-64
ABSTRACTWe introduce a model based on Ordinary Differential Equations to describe how two mutually exclusive groups progress through a career hierarchy, whether in a single organization, or in an entire economic sector. The intended application is to gender imbalance at the top of the academic hierarchy in European Universities; however, the model is entirely generic and may be applied in other contexts also. Previous research on gender imbalance in European universities has focused on large-scale statistical studies. Our model represents a point of departure, as it is deterministic (i.e., based on Ordinary Differential Equations). The model requires a precise definition of the progression rates for the different groups through the hierarchy; these are key parameters governing the dynamics of career progression. The progression rate for each group can be decomposed into a product: the proportion of group members at a low level in the hierarchy who compete for promotion to the next level a given year, multiplied by the in-competition success rate for the group in question. Either of these two parameters can differ across the groups under consideration; this introduces a group asymmetry into the organization’s composition. We introduce a glass-ceiling index to summarize this asymmetry succinctly. Using case studies from the literature, we demonstrate how the mathematical framework can pinpoint the proximate cause of the glass ceiling in European academia. 相似文献
46.
Impact of the Oxygen Defects and the Hydrogen Concentration on the Surface of Tetragonal and Monoclinic ZrO2 on the Reduction Rates of Stearic Acid on Ni/ZrO2 下载免费PDF全文
Sebastian Foraita Dr. John L. Fulton Zizwe A. Chase Aleksei Vjunov Pinghong Xu Dr. Eszter Baráth Dr. Donald M. Camaioni Dr. Chen Zhao Prof. Dr. Johannes A. Lercher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2423-2434
The role of the specific physicochemical properties of ZrO2 phases on Ni/ZrO2 has been explored with respect to the reduction of stearic acid. Conversion on pure m‐ZrO2 is 1.3 times more active than on t‐ZrO2, whereas Ni/m‐ZrO2 is three times more active than Ni/t‐ZrO2. Although the hydrodeoxygenation of stearic acid can be catalyzed solely by Ni, the synergistic interaction between Ni and the ZrO2 support causes the variations in the reaction rates. Adsorption of the carboxylic acid group on an oxygen vacancy of ZrO2 and the abstraction of the α‐hydrogen atom with the elimination of the oxygen atom to produce a ketene is the key to enhance the overall rate. The hydrogenated intermediate 1‐octadecanol is in turn decarbonylated to heptadecane with identical rates on all catalysts. Decarbonylation of 1‐octadecanol is concluded to be limited by the competitive adsorption of reactants and intermediate. The substantially higher adsorption of propionic acid demonstrated by IR spectroscopy and the higher reactivity to O2 exchange reactions with the more active catalyst indicate that the higher concentration of active oxygen defects on m‐ZrO2 compared to t‐ZrO2 causes the higher activity of Ni/m‐ZrO2. 相似文献
47.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
48.
This work describes a novel methodology for the recognition of brandies based on direct injection of a raw sample followed by GC-MS analysis. Direct injection was chosen for its simplicity and the fact that the composition of the samples analysed remains unchanged compared to original brandy. The repeatability of the analytical procedure was evaluated by a comparison of the peak areas for randomly selected compounds obtained from 10 parallel measurements. A novel chemometric procedure was investigated in order to separate the samples studied on the basis of their geographical origin, processing technology or maturation time. In this procedure, a principal component analysis was applied to full chromatograms to select the time interval that shows the significant differences between the samples studied. It was shown that the chromatogram recorded at 36–39 min bore the maximal differences, hence it could be used to classify the brandy samples. The chromatographic peaks found within this time interval were identified and their peak areas determined. These compounds could be used as specific markers for determining geographical origin or processing technology. 相似文献
49.
50.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献