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

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

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

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

A lithographic approach for quantum dot-photonic crystal nanocavity coupling in dilute nitrides

We report on a novel lithographic approach for the fabrication of integrated quantum dot (QD)-photonic crystal (PhC) nanocavity systems. We exploit unique hydrogen's ability to tailor the band gap energy of dilute nitride semiconductors to fabricate isolated site-controlled QDs via a spatially selective hydrogenation at the nanometer-scale. A deterministic integration of the realized site-controlled QDs with PhC nanocavities is provided by the inherent realignment precision (~ 20 nm) of the electron beam lithography system used for the fabrication of both QDs and PhC cavities. A detailed description of the fabrication steps leading to the realization of integrated QD-PhC cavity systems is provided, together with the experimental evidence of a weak coupling effect between the single-photon emitter and the PhC cavity

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 460$\:$GHz. 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 300$\:$mK. The measured average resonator $Q$s are 1.7$\times{10^4}$, 7.0$\times{10^4}$, 1.0$\times{10^4}$, and 1.0$\times{10^4}$ for the 150, 250, 350, and 460$\:$GHz arrays, respectively. The average electrical phase responsivities on resonance are 1.4$\:$rad/pW, 1.5$\:$rad/pW, 2.1$\:$rad/pW, and 2.1$\:$rad/pW; the electrical noise equivalent powers are 45$\:\rm{aW/\sqrt{Hz}}$, 160$\:\rm{aW/\sqrt{Hz}}$, 80$\:\rm{aW/\sqrt{Hz}}$, and 140$\:\rm{aW/\sqrt{Hz}}$, 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 NET$_{\rm RJ}$s are $200\:\mu\rm{K\sqrt{s}}$, $240\:\mu\rm{K\sqrt{s}}$, $240\:\mu\rm{K\sqrt{s}}$, and $\:340\mu\rm{K\sqrt{s}}$, 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

2,2,2-Tris(pyrazol-1-yl)ethanol

The title compound TPE, C11H12N6O, was prepared by slow evaporation from diethyl ether. In the crystal, there is a hydrogen bond between the alcohol H atom and an N in the pyrazole ring of a neighboring mol­ecule

BULLKID: Monolithic array of particle absorbers sensed by Kinetic Inductance Detectors

We introduce BULLKID, an innovative phonon detector consisting of an array of dices acting as particle absorbers sensed by multiplexed Kinetic Inductance Detectors (KIDs). The dices are carved in a thick crystalline wafer and form a monolithic structure. The carvings leave a thin common disk intact in the wafer, acting both as holder for the dices and as substrate for the KID lithography. The prototype presented consists of an array of 64 dices of 5.4x5.4x5 mm$^3$ carved in a 3" diameter, 5 mm thick silicon wafer, with a common disk 0.5 mm thick hosting a 60 nm patterned aluminum layer. The resulting array is highly segmented but avoids the use of dedicated holding structures for each unit. Despite the fact that the uniformity of the KID electrical response across the array needs optimization, the operation of 8 units with similar features shows, on average, a baseline energy resolution of $26\pm7$ eV. This makes it a suitable detector for low-energy processes such as direct interactions of dark matter and coherent elastic neutrino-nucleus scattering

Measuring CMB spectral distortions from Antarctica with COSMO: blackbody calibrator design and performance forecast

COSMO is a ground-based instrument to measure the spectral distortions (SD) of the Cosmic Microwave Background (CMB). In this paper, we present preliminary results of electromagnetic simulations of its reference blackbody calibrator. HFSS simulations provide a calibrator reflection coefficient of R∼ 10 - 6, corresponding to an emissivity ϵ= 1 - R= 0.999999. We also provide a forecast for the instrument performance by using an ILC-based simulation. We show that COSMO can extract the isotropic Comptonization parameter (modeled as | y| = 1.77 · 10 - 6) as | y| = (1.79 ± 0.19) · 10 - 6, in the presence of the main Galactic foreground (thermal dust) and of CMB anisotropies, and assuming perfect atmospheric emission removal