549 research outputs found
Copper and Zinc Metal–Organic Frameworks with Bipyrazole Linkers Display Strong Antibacterial Activity against Both Gram+ and Gram− Bacterial Strains
: Here, we report a new synthetic protocol based on microwave-assisted synthesis (MAS) for the preparation of higher yields of zinc and copper in MOFs based on different bis(pyrazolyl)-tagged ligands ([M(BPZ)]n where M = Zn(II), Cu(II), H2BPZ = 4,4'-bipyrazole, [M(BPZ-NH2)]n where M = Zn(II), Cu(II); H2BPZ-NH2 = 3-amino-4,4'-bipyrazole, and [Mx(Me4BPZPh)] where M = Zn(II), x = 1; Cu(II), x = 2; H2Me4BPZPh = bis-4'-(3',5'-dimethyl)-pyrazolylbenzene) and, for the first time, a detailed study of their antibacterial activity, tested against Gram-negative (E. coli) and Gram-positive (S. aureus) bacteria, as representative agents of infections. The results show that all MOFs exert a broad-spectrum activity and strong efficiency in bacterial growth inhibition, with a mechanism of action based on the surface contact of MOF particles with bacterial cells through the so-called "chelation effect" and reactive oxygen species (ROS) generation, without a significant release of Zn(II) and Cu(II) ions. In addition, morphological changes were elucidated by using a scanning electron microscope (SEM) and bacterial cell damage was further confirmed by a confocal laser scanning microscopy (CLSM) test
Steric and Electronic Effects Responsible for N, O- or N, N-Chelating Coordination of Pyrazolones Containing a Pyridine Ring in Ruthenium Arene Systems
Structural and electronic factors are crucial to rationalize the different N,O or N,N chelating coordination of pyrazolones containing a pyridine ring. The reactivity of proligand 3-phenyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,ph) with the (arene)Ru(II) fragment was explored. Neutral and ionic (arene)Ru(II) complexes were obtained and fully characterized, also by X-ray diffraction, revealing the ligand to coordinate in an unusual N,O-chelating fashion. Other ruthenium complexes were also synthesized with 3-methyl-1-(pyridin-2-yl)-5-pyrazolone (HLpy,me) and 3-methyl-1-(pyridin-2-yl)-4-trifluoroacetyl-5-pyrazolone (HQpy,CF3). In these complexes the ligands adopt the preferred N,N-chelating mode. Ligands and complexes were theoretically analyzed by density functional theory (DFT). The most stable tautomer of HLpy,phmatched well with the experimental behavior of this proligand and the structures of Ru-complexes were well described by calculations. The thermodynamic stability of the N,O- and N,N-coordination modes was analyzed and a proposal for the achievement of the N,O-coordination mode in complexes 1-4 was proposed. Cytotoxicity tests were performed against human ovarian carcinoma (A2780 and Cisplatin-resistant A2780cis) and nontumorigenic human embryonic kidney (HEK293T) cell lines, showing the free ligands to be more cytotoxic that the ensuing (arene)Ru(II) complexes
Executable Digital Process Twins: Towards the Enhancement of Process-Driven Systems
The development of process-driven systems and the advancements in digital twins have led to the birth of new ways of monitoring and analyzing systems, i.e., digital process twins. Specifically, a digital process twin can allow the monitoring of system behavior and the analysis of the execution status to improve the whole system. However, the concept of the digital process twin is still theoretical, and process-driven systems cannot really benefit from them. In this regard, this work discusses how to effectively exploit a digital process twin and proposes an implementation that combines the monitoring, refinement, and enactment of system behavior. We demonstrated the proposed solution in a multi-robot scenario
Herramientas para el seguimiento de procesos de interactividad mediatizados por facebook en educación superior
Esta ponencia presenta diversas herramientas para el seguimiento y evaluación de procesos de interactividad mediatizados por Facebook que pueden utilizarse para el análisis de propuestas educativas de nivel superior. A tal fin, fue necesario precisar y profundizar los conceptos de redes sociales y sus herramientas de análisis existentes. Enmarcados en la noción de Dispositivo Hipermedial Dinámico como una propuesta innovadora para construir aprendizajes significativos, abordamos dichos instrumentos tecnológicos con la clara finalidad de analizar su utilización y su capacidad real. Aunque Facebook tuvo su origen en un ambiente específicamente universitario, se evidencia que la mayoría de estas aplicaciones carecen de especificidad para un enfoque educativo y orientan su finalidad a contextos comerciales o de mercado. Sin embargo, existe un grupo reducido de estas cuyos resultados pueden aportar elementos de análisis, como así también algunos desarrollos a nivel prototipo que podrían aportar soluciones originales.Eje: Workshop Tecnología informática aplicada en educación (WTIAE)Red de Universidades con Carreras en Informática (RedUNCI
Spontaneous self-assembly of an unsymmetric trinuclear triangular copper(II) pyrazolate complex, [Cu3(μ3-OH)(μ-pz) 3(MeCOO)2(Hpz)] (Hpz = pyrazole). Synthesis, experimental and theoretical characterization, reactivity, and catalytic activity
The almost quantitative formation of the triangular trinuclear copper derivative [Cu3(μ3-OH)(μ-pz)3(MeCOO) 2(Hpz)] (1) (Hpz = pyrazole), has been simply achieved by adding Hpz to an ethanol solution of Cu(MeCOO)2·H2O. An X-ray molecular structure determination shows that 1 is completely unsymmetric and that trinuclear units result assembled in an extended bidimensional network formed through acetate bridges and hydrogen bonds. EPR and magnetic measurements are consistent with the presence of a single unpaired electron. Theoretical density functional calculations carried out for S = 1/2 provide a thorough description of the electronic structure of 1, allowing a detailed assignment of its UV-vis absorption spectrum. Compound 1 reacts with MeONa, yielding [Cu 3(μ3-OH)(μ-pz)3(MeCOO)(MeO)(Hpz)] (2) and [Cu3(μ3-OH)(μ-pz)3(MeO) 2(Hpz)] (3) through the substitution of one and two acetate ions, respectively, with MeO- ion(sS). The spontaneous self-assembly of the triangular trinuclear Cu3 moiety seems to occur only with pyrazole as can be inferred by the results obtained in the reactions of copper(II) acetate with some substituted pyrazoles leading to the formation of mononuclear [Cu(MeCOO)2(L)2] (4-8) and dinuclear [Cu(MeCOO) 2(L)]2 (9-11) (L = substituted pyrazole) compounds. Also the presence of acetate ions seems to play a leading role in determining the formation of the trinuclear triangular arrangement, as indicated by the formation of a mononuclear derivative, [Cu(CF3COO) 2(Hpz)]2 (compound 12), in the reaction of copper(II) trifluoroacetate with pyrazole. Compounds 1-3, as well as some other mono- and dinuclear copper(II)-substituted pyrazole complexes, have been tested as catalyst precursors in cyclopropanation reaction, observing the formation of products in a syn:anti ratio opposite that normally reported
Phonon and light read out of a Li 2MoO 4 crystal with multiplexed kinetic inductance detectors
Molybdenum based crystals such as Li 2MoO 4 and CaMoO4 are emerging as leading candidates for next generation experiments searching for neutrino-less double beta decay with cryogenic calorimeters (CUPID, AMoRE). The exquisite energy resolution and high radio-purity of these crystals come at the cost of a potentially detrimental background source: the two neutrinos double beta decay of 100Mo. Indeed, the fast half-life of this decay mode, combined with the slow response of cryogenic calorimeters, would result in pile-up events in the energy region of interest for neutrino-less double beta decay, reducing the experimental sensitivity. This background can be suppressed using fast and high sensitivity cryogenic light detectors, provided that the scintillation time constant itself does not limit the time resolution. We developed a new detection technique exploiting the high sensitivity, the fast time response and the multiplexing capability of Kinetic Inductance Detectors. We applied the proposed technique to a 2 × 2 × 2 cm3Li 2MoO 4 crystal, which was chosen as baseline option for CUPID. We measured simultaneously both the phonon and scintillation signals with KIDs. We derived the scintillation time constant of this compound at millikelvin temperatures obtaining tscint= 84.5 ± 4.5 (syst) ± 1.0 (stat) µs, constant between 10 and 190 mK
Reducing the impact of radioactivity on quantum circuits in a deep-underground facility
As quantum coherence times of superconducting circuits have increased from
nanoseconds to hundreds of microseconds, they are currently one of the leading
platforms for quantum information processing. However, coherence needs to
further improve by orders of magnitude to reduce the prohibitive hardware
overhead of current error correction schemes. Reaching this goal hinges on
reducing the density of broken Cooper pairs, so-called quasiparticles. Here, we
show that environmental radioactivity is a significant source of nonequilibrium
quasiparticles. Moreover, ionizing radiation introduces time-correlated
quasiparticle bursts in resonators on the same chip, further complicating
quantum error correction. Operating in a deep-underground lead-shielded
cryostat decreases the quasiparticle burst rate by a factor fifty and reduces
dissipation up to a factor four, showcasing the importance of radiation
abatement in future solid-state quantum hardware
Kinetic Inductance Detectors for the OLIMPO experiment: design and pre-flight characterization
We designed, fabricated, and characterized four arrays of horn--coupled,
lumped element kinetic inductance detectors (LEKIDs), optimized to work in the
spectral bands of the balloon-borne OLIMPO experiment. OLIMPO is a 2.6 m
aperture telescope, aimed at spectroscopic measurements of the
Sunyaev-Zel'dovich (SZ) effect. OLIMPO will also validate the LEKID technology
in a representative space environment. The corrected focal plane is filled with
diffraction limited horn-coupled KID arrays, with 19, 37, 23, 41 active pixels
respectively at 150, 250, 350, and 460GHz. Here we report on the full
electrical and optical characterization performed on these detector arrays
before the flight. In a dark laboratory cryostat, we measured the resonator
electrical parameters, such as the quality factors and the electrical
responsivities, at a base temperature of 300mK. The measured average
resonator s are 1.7, 7.0, 1.0, and
1.0 for the 150, 250, 350, and 460GHz arrays, respectively.
The average electrical phase responsivities on resonance are 1.4rad/pW,
1.5rad/pW, 2.1rad/pW, and 2.1rad/pW; the electrical noise
equivalent powers are 45, 160,
80, and 140, at 12 Hz. In the OLIMPO
cryostat, we measured the optical properties, such as the noise equivalent
temperatures (NET) and the spectral responses. The measured NETs are
, , ,
and , at 12 Hz; under 78, 88, 92, and 90 mK
Rayleigh-Jeans blackbody load changes respectively for the 150, 250, 350, and
460 GHz arrays. The spectral responses were characterized with the OLIMPO
differential Fourier transform spectrometer (DFTS) up to THz frequencies, with
a resolution of 1.8 GHz.Comment: Published on JCA
A Target Animal Effectiveness Study on Adjuvant Peptide-Based Vaccination in Dogs with Non-Metastatic Appendicular Osteosarcoma Undergoing Amputation and Chemotherapy
Despite efforts to develop novel treatment strategies, human and canine osteosarcomas continue to have poor prognosis and limited overall survival. The aim of this clinical trial was to test the antitumor effect and safety of multiple dermal administrations of a peptide-based anticancer vaccine in dogs with non-metastatic appendicular osteosarcoma undergoing standard of care (SOC), consisting of limb amputation and adjuvant chemotherapy. Salmonella-infected canine osteosarcoma cells were induced to release immunogenic peptides in the extracellular space via Cx43 hemichannels opening; the secretome was collected and constituted the vaccine. Dogs with non-metastatic appendicular osteosarcoma were eligible for recruitment. Following limb amputation and adjuvant carboplatin, dogs were vaccinated on a monthly basis for six times and followed up with serial thoracic radiographs. A population of dogs undergoing SOC treatment (amputation and adjuvant carboplatin) before the vaccine was available served as controls. Primary endpoints were time to metastasis (TTM) and tumor-specific survival (TSS). Secondary endpoints were feasibility, toxicity, T-cell and humoral immune responses. A total of 20 dogs were vaccinated along with SOC and 34 received SOC only. Vaccine-specific humoral and T-cell responses were observed; their amplitude correlated with TSS. Vaccine-associated toxicity was not recorded. TTM and TSS were significantly longer in vaccinated versus unvaccinated dogs (TTM: 308 vs. 240 days, respectively; p = 0.010; TSS: 621 vs. 278 days, respectively; p = 0.002). In dogs with non-metastatic osteosarcoma undergoing SOC, the addition of a bacteria-based vaccination strategy increased TTM, thereby prolonging survival, while maintaining a safe profile. Additionally, vaccinated dogs developed a long-term tumor-specific response, as documented by the immunomonitoring of these patients over time. These results hold promise for future management of canine osteosarcoma
Aerosol-assisted chemical vapour deposition of transparent superhydrophobic film by using mixed functional alkoxysilanes
A method for the preparation of transparent superhydrophobic silica coatings on glass substrates via aerosol‐assisted chemical vapour deposition (AACVD) is described. A multi-layer process to produce dual scale silica nanoparticles films, by using different functional alkoxysilanes was investigated. A first layer of 3-methacryloxypropyltrimethoxysilane (MPS) and a second layer of tetraethylorthosilicate (TEOS) were deposited at different temperatures to generate micro and nano particles of silica. Finally, a layer of perfluorooctyltriethoxysilane was deposited on top of the two layers to achieve superhydrophobicity. The transparent superhydrophobic film showed transparency of 90% in the visible light region with a static water contact angle of 165° and a sliding angle lower than 1°. Various durability tests were performed on the transparent superhydrophobic film, showing a constant water repellency after corrosion and organic solvents tests, strong resistance under UV light, and thermal stability up to 400 °C. Sandpaper mechanical robustness durability test showed superhydrophobicity for up to 5 rubbing cycles. In this study, a novel strategy to achieve highly transparent superhydrophobic glass surfaces using AACVD of alkoxysilanes, to produce surfaces with excellent durability is described. This shows great potential to obtain silica superhydrophobic films for large–scale applications
- …