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91.
Multifunctional Supramolecular Dendrimers with an s‐Triazine Ring as the Central Core: Liquid Crystalline,Fluorescence and Photoconductive Properties 下载免费PDF全文
Madalina Bucoş Dr. Teresa Sierra Dr. Attilio Golemme Dr. Roberto Termine Dr. Joaquín Barberá Dr. Raquel Giménez Prof. Dr. José Luis Serrano Dr. Pilar Romero Dr. Mercedes Marcos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10027-10037
Novel liquid crystal (LC) dendrimers have been synthesised by hydrogen bonding between an s‐triazine as the central core and three peripheral dendrons derived from bis(hydroxymethyl)propionic acid. Symmetric acid dendrons bearing achiral promesogenic units have been synthesised to obtain 3:1 complexes with triazine that exhibit LC properties. Asymmetric dendrons that combine the achiral promesogenic unit and an active moiety derived from coumarin or pyrene structures have been synthesised in order to obtain dendrimers with photophysical and electrochemical properties. The formation of the complexes was confirmed by IR and NMR spectroscopy data. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy and X‐ray diffractometry. All complexes displayed mesogenic properties, which were smectic in the case of symmetric dendrons and their complexes and nematic in the case of asymmetric dendrons and their dendrimers. A supramolecular model for the lamellar mesophase, based mainly on X‐ray diffraction studies, is proposed. The electrochemical behaviour of dendritic complexes was investigated by cyclic voltammetry. The UV/Vis absorption and emission properties of the compounds and the photoconductive properties of the dendrons and dendrimers were also investigated 相似文献
92.
The π‐Back‐Bonding Modulation and Its Impact in the Electronic Properties of CuII Antineoplastic Compounds: An Experimental and Theoretical Study 下载免费PDF全文
Juan Carlos García‐Ramos Dr. Rodrigo Galindo‐Murillo Araceli Tovar‐Tovar Ana Luisa Alonso‐Saenz Virginia Gómez‐Vidales Dr. Marcos Flores‐Álamo Dr. Luis Ortiz‐Frade Dr. Fernando Cortes‐Guzmán Dr. Rafael Moreno‐Esparza Prof. Antonio Campero Prof. Lena Ruiz‐Azuara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13730-13741
93.
Marcos A. Kettner Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Thomas M. Klapötke Dr. Muhamed Sućeska Swetlana Wunder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7622-7631
Here we report on the preparation of two hydrogen atom free 3,3′‐bi(1,2,4‐oxadiazole) derivatives. 5,5′‐Bis(fluorodinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole) was synthesised by fluorination of diammonium 5,5′‐bis(dinitromethanide)‐3,3′‐bi(1,2,4‐oxadiazole). For our previously reported analogue 5,5′‐bis(trinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole), a new synthetic route starting from new 3,3′‐bi(1,2,4‐oxadiazolyl)‐5,5′‐diacetic acid was developed. In this course also hitherto unknown 5,5′‐dimethyl‐3,3′‐bi(1,2,4‐oxadiazole) was isolated. The compounds were characterised by multinuclear NMR spectroscopy, IR and Raman spectroscopy, elemental analysis as well as mass spectrometry. X‐ray diffraction studies were performed and the crystal structures for the 5,5'‐dimethyl and 5,5'‐(fluorodinitromethyl) derivatives are reported. The energetic 5,5'‐(fluorodinitromethyl) and 5,5'‐(trinitromethyl) compounds do not contain any hydrogen atoms and show remarkable high densities. Furthermore, the thermal stabilities and sensitivities were determined by differential scanning calorimetry (DSC) and standardised impact and friction tests. The heats of formation were calculated by the atomisation method based on CBS‐4M enthalpies. With these values and the room‐temperature X‐ray densities, several detonation and propulsion parameters, such as the detonation velocity and pressure as well as the specific impulse of mixtures with aluminium, were computed using the EXPLO5 code. 相似文献
94.
Control of the Electronic Ground State on an Electron‐Transfer Copper Site by Second‐Sphere Perturbations 下载免费PDF全文
Marcos N. Morgada Dr. Luciano A. Abriata Ulises Zitare Dr. Damian Alvarez‐Paggi Prof. Daniel H. Murgida Prof. Alejandro J. Vila 《Angewandte Chemie (International ed. in English)》2014,53(24):6188-6192
The CuA center is a dinuclear copper site that serves as an optimized hub for long‐range electron transfer in heme–copper terminal oxidases. Its electronic structure can be described in terms of a σu* ground‐state wavefunction with an alternative, less populated ground state of πu symmetry, which is thermally accessible. It is now shown that second‐sphere mutations in the CuA containing subunit of Thermus thermophilus ba3 oxidase perturb the electronic structure, which leads to a substantial increase in the population of the πu state, as shown by different spectroscopic methods. This perturbation does not affect the redox potential of the metal site, and despite an increase in the reorganization energy, it is not detrimental to the electron‐transfer kinetics. The mutations were achieved by replacing the loops that are involved in protein–protein interactions with cytochrome c, suggesting that transient protein binding could also elicit ground‐state switching in the oxidase, which enables alternative electron‐transfer pathways. 相似文献
95.
Marcos Vilario Josune García-Sanmartín Laura Ochoa-Callejero Alberto Lpez-Rodríguez Jaime Blanco-Urgoiti Alfredo Martínez 《Molecules (Basel, Switzerland)》2020,25(24)
Mushrooms have been used for millennia as cancer remedies. Our goal was to screen several mushroom species from the rainforests of Costa Rica, looking for new antitumor molecules. Mushroom extracts were screened using two human cell lines: A549 (lung adenocarcinoma) and NL20 (immortalized normal lung epithelium). Extracts able to kill tumor cells while preserving non-tumor cells were considered “anticancer”. The mushroom with better properties was Macrocybe titans. Positive extracts were fractionated further and tested for biological activity on the cell lines. The chemical structure of the active compound was partially elucidated through nuclear magnetic resonance, mass spectrometry, and other ancillary techniques. Chemical analysis showed that the active molecule was a triglyceride containing oleic acid, palmitic acid, and a more complex fatty acid with two double bonds. The synthesis of all possible triglycerides and biological testing identified the natural compound, which was named Macrocybin. A xenograft study showed that Macrocybin significantly reduces A549 tumor growth. In addition, Macrocybin treatment resulted in the upregulation of Caveolin-1 expression and the disassembly of the actin cytoskeleton in tumor cells (but not in normal cells). In conclusion, we have shown that Macrocybin constitutes a new biologically active compound that may be taken into consideration for cancer treatment. 相似文献
96.
Marcos V. Foguel Angelica M. Balcarcel Mark A. Reed Percy Calvo‐Marzal Yulia V. Gerasimova Dmitry M. Kolpashchikov Karin Y. Chumbimuni‐Torres 《Electroanalysis》2020,32(4):835-841
One major challenge in nucleic acids analysis by hybridization probes is a compromise between the probe's tight binding and sequence‐selective recognition of nucleic acid targets folded into stable secondary structures. We have been developing a four‐way junction (4WJ)‐based sensor that consists of a universal stem‐loop (USL) probe immobilized on an electrode surface and two adaptor strands (M and F). The sensor was shown to be highly selective towards single base mismatches at room temperature, able to detect multiple targets using the same USL probe, and have improved ability to detect folded nucleic acids. However, some nucleic acid targets, including natural RNA, are folded into very stable secondary and tertiary structures, which may represent a challenge even for the 4WJ sensors. This work describes a new sensor, named MVF since it uses three probe stands M, V and F, which further improves the performance of 4WJ sensors with folded targets. The MVF sensor interrogating a 16S rRNA NASBA amplicon with calculated folding energy of ?32.82 kcal/mol has demonstrated 2.5‐fold improvement in a signal‐to‐background ratio in comparison with a 4WJ sensor lacking strand V. The proposed design can be used as a general strategy in the analysis of folded nucleic acids including natural RNA. 相似文献
97.
Beatriz Lozano‐Torres Juan F. Blandez Irene Galiana Alba García‐Fernndez María Alfonso María D. Marcos Mar Orzez Flix Sancenn Ramn Martínez‐Mez 《Angewandte Chemie (International ed. in English)》2020,59(35):15152-15156
In vivo detection of cellular senescence is accomplished by using mesoporous silica nanoparticles loaded with the NIR‐FDA approved Nile blue (NB) dye and capped with a galactohexasaccharide ( S3 ). NB emission at 672 nm is highly quenched inside S3 , yet a remarkable emission enhancement is observed upon cap hydrolysis in the presence of β‐galactosidase and dye release. The efficacy of the probe to detect cellular senescence is tested in vitro in melanoma SK‐Mel‐103 and breast cancer 4T1 cells and in vivo in palbociclib‐treated BALB/cByJ mice bearing breast cancer tumor. 相似文献
98.
99.
Lana Mara Rodrigues dos Santos Philippe Michelon Marcos Nereu Arenales Ricardo Henrique Silva Santos 《Annals of Operations Research》2011,190(1):165-180
In this article we propose a 0-1 optimization model to determine a crop rotation schedule for each plot in a cropping area.
The rotations have the same duration in all the plots and the crops are selected to maximize plot occupation. The crops may
have different production times and planting dates. The problem includes planting constraints for adjacent plots and also
for sequences of crops in the rotations. Moreover, cultivating crops for green manuring and fallow periods are scheduled into
each plot. As the model has, in general, a great number of constraints and variables, we propose a heuristics based on column
generation. To evaluate the performance of the model and the method, computational experiments using real-world data were
performed. The solutions obtained indicate that the method generates good results. 相似文献
100.
da Silva Jussara Vieira Madurro Ana Graci Brito Madurro João Marcos 《Journal of Solid State Electrochemistry》2017,21(7):2129-2139
Journal of Solid State Electrochemistry - This paper reports a new platform for oligonucleotide hybridization, prepared by electropolymerization of 3-hydroxyphenylacetic acid onto gold electrode... 相似文献