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211.
Orte A Talavera EM Maçanita AL Orte JC Alvarez-Pez JM 《The journal of physical chemistry. A》2005,109(39):8705-8718
2',7'-Difluorofluorescein (Oregon Green 488, OG488) is a novel fluorescein dye derivative which presents important advantages for improving the fluorimetric applications in the biomedical and biochemical sciences. In aqueous solution it displays four prototropic forms, namely cation (C), neutral (N), monoanion (M), and dianion (D). In previous works, we found (J. Phys. Chem. A 2005, 109, 734-747, 2840-2846) that OG488 undergoes excited-state proton transfer reactions, which may affect the results from applications using this dye. We established that the excited-state proton transfer (ESPT) reactions between neutral, monoanionic, and dianionic forms of OG488 are promoted by acetate buffer, and we characterized the ground and excited species involved. We also solved the kinetics of the prototropic reactions using global compartmental analysis. In the present paper, we extend our study on the ESPT reactions of OG488 to acidic media, in which only the three prototropic species cation, neutral, and monoanion coexist. We have solved the kinetics of the three-state ESPT reaction by means of global three-compartmental analysis of a fluorescence decay surface in moderately acidic media (pH between 1.1 and 3.0), recovering the kinetic and spectral parameters of this three-state system. This system is one of the most complex solved to date, due to the strong overlap of the absorption and emission spectra of the neutral and monoanionic forms of OG488. We also found that the cation behaves as "super" photoacid, showing a very high deprotonation rate constant (1.04 x 10(11) s(-1)) and an enhanced acidity. Therefore, we also carried out experiments at very high perchloric acid concentrations, dealing with some other effects which become noteworthy at these [H(+)]. The presence of xanthylium cation quenching due to "free" water molecules, and the reduction in the amount of water clusters acting as proton acceptors, are processes which alter notably the time course of the excited-species in this high [H(+)] range. 相似文献
212.
Mineral content and botanical origin of Spanish honeys 总被引:2,自引:0,他引:2
Fernández-Torres R Pérez-Bernal JL Bello-López MA Callejón-Mochón M Jiménez-Sánchez JC Guiraúm-Pérez A 《Talanta》2005,65(3):686-691
Eleven elements (Zn, P, B, Mn, Mg, Cu, Ca, Ba, Sr, Na and K) were determined by inductively plasma coupled spectrometry in 40 honey samples from different places of Spain and four different botanical origins: Eucalyptus (Eucalyptus sp.), Heather (Erica sp.), Orange-blossom (Citrus sinensis) and Rosemary (Rosmarinus officinalis). K, Ca and P show the higher levels with average concentrations ranged between 434.1-1935 mg kg−1 for K; 42.59-341.0 mg kg−1 for Ca and 51.17-154.3 mg kg−1 for P. Levels of Cu (0.531-2.117 mg kg−1), Ba (0.106-1.264 mg kg−1) and Sr (0.257-1.462 mg kg−1) are the lowest in all honey samples. Zn (1.332-7.825 mg kg−1), Mn (0.133-9.471 mg kg−1), Mg (13.26-74.38 mg kg−1) and Na (11.69-218.5 mg kg−1) concentrations were found strongly dependent on the kind of botanical origin.Results were submitted to pattern recognition procedures, unsupervised methods such as cluster and principal components analysis and supervised learning methods like linear discriminant analysis in order to evaluate the existence of data patterns and the possibility of differentiation of Spanish honeys from different botanical origins according to their mineral content. Cluster analysis shows four clusters corresponding to the four botanical origins of honey and PCA explained 71% of the variance with the first two PC variables. The best-grouped honeys were those from heather; eucalyptus honeys formed a more dispersed group and finally orange-blossom and rosemary honeys formed a less distinguishable group. 相似文献
213.
Prof. Juan Carlos López Dr. Alberto Macario Prof. Assimo Maris Prof. Ibon Alkorta Prof. Susana Blanco 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(55):13870-13878
The rotational spectrum of the weakly bound complex pentafluoropyridine⋅⋅⋅formaldehyde has been investigated using Fourier transform microwave spectroscopy. From the analysis of the rotational parameters of the parent species and of the 13C and 15N isotopologues, the structural arrangement of the adduct has been unambiguously established. The full ring fluorination of pyridine has a dramatic effect on its binding properties: It alters the electron density distribution at the π-cloud of pyridine creating a π-hole and changing its electron donor-acceptor capabilities. In the complex, formaldehyde lies above the aromatic ring with one of the oxygen lone pairs, as conventionally envisaged, pointing toward its centre. This lone pair⋅⋅⋅π-hole interaction, reinforced by a weak C−H⋅⋅⋅N interaction, indicates an exchange of the electron-acceptor roles of both molecules when compared to the pyridine⋅⋅⋅formaldehyde adduct. Tunnelling doublets due to the internal rotation of formaldehyde have also been observed and analysed leading to a discussion on the competition between lone pair⋅⋅⋅π-hole and π⋅⋅⋅π stacking interactions. 相似文献
214.
Lidia Moreira Lima Tiago Fernandes da Silva Carlos Eduardo da Silva Monteiro Cristiane Aparecida-Silva Walfrido Bispo Júnior Aline Cavalcanti de Queiroz Magna Suzana Alexandre-Moreira Gisele Zapata-Sudo Eliezer J. Barreiro 《Molecules (Basel, Switzerland)》2021,26(16)
Acylhydrazones are still an important framework to the design of new bioactive compounds. As treatment of chronic pain represents a clinical challenge, we decided to modify the structure of LASSBio-1514 (1), previously described as anti-inflammatory and analgesic prototype. Applying the homologation as a strategy for molecular modification, we designed a series of cyclopentyl- (2a–e), cyclobutyl- (3a–e), and cyclopropylacylhydrazones (4a–e) that were synthetized and evaluated in murine models of inflammation and pain. A comparison of their in silico physicochemical and drug-like profile was conducted, as well as their anti-inflammatory and analgesic effect. Compounds 4a (LASSBio-1755) and 4e (LASSBio-1757) displayed excellent in silico drug-like profiles and were identified as new analgesic lead-candidates in acute and chronic model of pain, through oral administration. 相似文献
215.
Arlindo Csar Matias Pereira Helison de Oliveira Carvalho Danna Emanuelle Santos Gonalves Karyny Roberta Tavares Picano Abraho Victor Tavares de Lima Teixeira dos Santos Heitor Ribeiro da Silva Francinaldo Sarges Braga Roberto Messias Bezerra Alessandro de Sousa Nunes Maira Tiyomi Sacata Tongo Nazima Júlia Gomes Cerqueira Talisson Taglialegna Janayra Maris Teixeira Jos Carlos Tavares Carvalho 《Molecules (Basel, Switzerland)》2021,26(16)
This study aimed to evaluate and compare the effects of co-treatment with purified annatto oil (PAO) or its granules (GRA, Chronic®) with that of testosterone on the orchiectomy-induced osteoporosis in Wistar rats. After surgery, rats were treated from day 7 until day 45 with testosterone only (TES, 7 mg/kg, IM) or TES + PAO or GRA (200 mg/kg, p.o.). The following parameters were evaluated: food/water intake, weight, HDL, LDL, glucose, triglycerides (TG), total cholesterol (TC), alkaline phosphatase levels, blood phosphorus and calcium contents, femur weight, structure (through scanning electron microscopy), and calcium content (through atomic absorption spectrophotometry). Our results show that orchiectomy could significantly change the blood lipid profile and decrease bone integrity parameters. Testosterone reposition alone could improve some endpoints, including LDL, TC, bone weight, and bone calcium concentration. However, other parameters were not significantly improved. Co-treatment with PAO or GRA improved the blood lipid profile and bone integrity more significantly and improved some endpoints not affected by testosterone reposition alone (such as TG levels and trabeculae sizes). The results suggest that co-treatment with annatto products improved the blood lipid profile and the anti-osteoporosis effects of testosterone. Overall, GRA had better results than PAO. 相似文献
216.
Jorge Ivn Castro Manuel N. Chaur Carlos Humberto Valencia Llano Mayra Eliana Valencia Zapata Jos Herminsul Mina Hernandez Carlos David Grande-Tovar 《Molecules (Basel, Switzerland)》2021,26(16)
In recent decades, the number of patients requiring biocompatible and resistant implants that differ from conventional alternatives dramatically increased. Among the most promising are the nanocomposites of biopolymers and nanomaterials, which pretend to combine the biocompatibility of biopolymers with the resistance of nanomaterials. However, few studies have focused on the in vivo study of the biocompatibility of these materials. The electrospinning process is a technique that produces continuous fibers through the action of an electric field imposed on a polymer solution. However, to date, there are no reports of chitosan (CS) and polyvinyl alcohol (PVA) electrospinning with carbon nano-onions (CNO) for in vivo implantations, which could generate a resistant and biocompatible material. In this work, we describe the synthesis by the electrospinning method of four different nanofibrous membranes of chitosan (CS)/(PVA)/oxidized carbon nano-onions (ox-CNO) and the subdermal implantations after 90 days in Wistar rats. The results of the morphology studies demonstrated that the electrospun nanofibers were continuous with narrow diameters (between 102.1 nm ± 12.9 nm and 147.8 nm ± 29.4 nm). The CS amount added was critical for the diameters used and the successful electrospinning procedure, while the ox-CNO amount did not affect the process. The crystallinity index was increased with the ox-CNO introduction (from 0.85% to 12.5%), demonstrating the reinforcing effect of the nanomaterial. Thermal degradation analysis also exhibited reinforcement effects according to the DSC and TGA analysis, with the higher ox-CNO content. The biocompatibility of the nanofibers was comparable with the porcine collagen, as evidenced by the subdermal implantations in biological models. In summary, all the nanofibers were reabsorbed without a severe immune response, indicating the usefulness of the electrospun nanocomposites in biomedical applications. 相似文献
217.
Danillo Valverde Adalberto V. S. de Araújo Antonio Carlos Borin 《Molecules (Basel, Switzerland)》2021,26(17)
The photophysical relaxation mechanisms of 1-cyclohexyluracil, in vacuum and water, were investigated by employing the Multi-State CASPT2 (MS-CASPT2, Multi-State Complete Active-Space Second-Order Perturbation Theory) quantum chemical method and Dunning’s cc-pVDZ basis sets. In both environments, our results suggest that the primary photophysical event is the population of the bright state. Afterwards, two likely deactivation pathways can take place, which is sustained by linear interpolation in internal coordinates defined via Z-Matrix scans connecting the most important characteristic points. The first one (Route 1) is the same relaxation mechanism observed for uracil, its canonical analogue, i.e., internal conversion to the ground state through an ethylenic-like conical intersection. The other route (Route 2) is the direct population transfer from the bright state to the triplet state via an intersystem crossing process involving the (/) singlet-triplet crossing point. As the spin-orbit coupling is not too large in either environment, we propose that most of the electronic population initially on the state returns to the ground following the same ultrafast deactivation mechanism observed in uracil (Route 1), while a smaller percentage goes to the triplet manifold. The presence of a minimum on the potential energy hypersurface in water can help to understand why experimentally it is noticed suppression of the triplet states population in polar protic solvent. 相似文献
218.
Villagomez-Guzman Ana K. Rodriguez-Garcia Gabriela del Rio Rosa E. Oliveros Ortiz Antonio J. Cerda-Garcia-Rojas Carlos M. Joseph-Nathan Pedro Gomez-Hurtado Mario A. 《Chemistry of Natural Compounds》2021,57(2):319-322
Chemistry of Natural Compounds - A known kaurenoic acid (1), together with a new kaurane derivative named 3α-isobutyryloxykaurenoic acid (2), was isolated from the roots of Lasianthaea aurea,... 相似文献
219.
Vartika Srivastava Manukonda Suresh Kumar Puthiya Veetil Nidheesh Carlos A. Martínez-Huitle 《Current Opinion in Electrochemistry》2021
Use of robust and safe water disinfection technologies which are inexpensive and energy-efficient are need of the hour to combat the problem of inadequate access of safe and clean drinking water. Energy and chemically intensive water treatment technologies warrant the need for a safe and environmentally sound treatment technology. Electrochemical disinfection or electrodisinfection (ED) is experiencing a great resurgence among the scientific communities owing to its novel use of electrode materials and electric current in an inexpensive and energy-efficient way for achieving the inactivation of microorganisms. Among the various electrodes used in the ED, boron-doped diamonds emerge as a sustainable alternate for their ability to electro generate strong potent oxidants which result in effective pathogen control in drinking water. ED for disinfecting waters occurs via generation of the reactive species which act in the bacterial inactivation mechanisms. In this mini-review, a critical discussion on the fundamentals and applications of promising electrochemical methods using boron-doped diamond anodes (namely electrochemical oxidation), evidencing their advantages for the remediation of drinking water infected with waterborne agents, is given. 相似文献
220.
Molins Elies Roig Anna Miravitlles Carlos Moreno-Mañas Marcial Vallribera Adelina Gálvez Nicanor Serra Neus 《Structural chemistry》1998,9(3):203-208
The crystal and molecular structure of (BzlMe3N)
2
+
[Fe2OCl6]2- has been determined. The asymmetric unit contains two benzyltrimethylammonium cations and two half -oxo-bis(trichloro-iron(III)) anions. The bridging -oxygen atoms of these anions are located over crystallographic symmetry elements. Therefore, the two anions resulting from the symmetry operations correspond to two different conformers presenting angular and linear dispositions of the Fe-O-Fe bond angle. Mössbauer spectrum consists of two asymmetric lines that are adequately simulated by two equally populated quadrupole doublets associated with the two iron sites. 相似文献