Interpretation of NMR Relaxation as a Tool for Characterising the Adsorption Strength of Liquids inside Porous Materials

Nuclear magnetic resonance (NMR) relaxation times are shown to provide a unique probe of adsorbate–adsorbent interactions in liquid‐saturated porous materials. A short theoretical analysis is presented, which shows that the ratio of the longitudinal to transverse relaxation times (T₁/T₂) is related to an adsorbate–adsorbent interaction energy, and we introduce a quantitative metric e_surf (based on the relaxation time ratio) characterising the strength of this surface interaction. We then consider the interaction of water with a range of oxide surfaces (TiO₂ anatase, TiO₂ rutile, γ‐Al₂O₃, SiO₂, θ‐Al₂O₃ and ZrO₂) and show that e_surf correlates with the strongest adsorption sites present, as determined by temperature programmed desorption (TPD). Thus we demonstrate that NMR relaxation measurements have a direct physical interpretation in terms of the characterisation of activation energy of desorption from the surface. Further, for a series of chemically similar solid materials, in this case a range of oxide materials, for which at least two calibration values are obtainable by TPD, the e_surf parameter yields a direct estimate of the maximum activation energy of desorption from the surface. The results suggest that T₁/T₂ measurements may become a useful addition to the methods available to characterise liquid‐phase adsorption in porous materials. The particular motivation for this work is to characterise adsorbate–surface interactions in liquid‐phase catalysis.     

From a Medicinal Mushroom Blend a Direct Anticancer Effect on Triple-Negative Breast Cancer: A Preclinical Study on Lung Metastases

Bioactive metabolites isolated from medicinal mushrooms (MM) used as supportive treatment in conventional oncology have recently gained interest. Acting as anticancer agents, they interfere with tumor cells and microenvironment (TME), disturbing cancer development/progression. Nonetheless, their action mechanisms still need to be elucidated. Recently, using a 4T1 triple-negative mouse BC model, we demonstrated that supplementation with Micotherapy U-Care, a MM blend, produced a striking reduction of lung metastases density/number, paralleled by decreased inflammation and oxidative stress both in TME and metastases, together with QoL amelioration. We hypothesized that these effects could be due to either a direct anticancer effect and/or to a secondary/indirect impact of Micotherapy U-Care on systemic inflammation/immunomodulation. To address this question, we presently focused on apoptosis/proliferation, investigating specific molecules, i.e., PARP1, p53, BAX, Bcl2, and PCNA, whose critical role in BC is well recognized. We revealed that Micotherapy U-Care is effective to influence balance between cell death and proliferation, which appeared strictly interconnected and inversely related (p53/Bax vs. Bcl2/PARP1/PCNA expression trends). MM blend displayed a direct effect, with different efficacy extent on cancer cells and TME, forcing tumor cells to apoptosis. Yet again, this study supports the potential of MM extracts, as adjuvant supplement in the TNBC management.     

Conical harmonic generation in isotropic materials

A novel class of nonlinear optical processes is described in which radiation at the nth harmonic is generated through the use of a (2n+1)-order nonlinearity. Utilizing an odd-order nonlinearity, this process allows for the generation and amplification of both odd- and even-order harmonics in isotropic materials. Additionally, this process can always be phase matched in normal-dispersion materials without the use of birefringence. Experimental results are presented in which conical third-harmonic emission is generated from a sapphire sample.     

Excited levels of 233Pa by alpha decay of 237Np

α-spectrometry using Si(Au) detectors has been performed with thin samples of ²³⁷Np; αγ bi-parametric coincidences have permitted an analysis and unfolding of the spectrum and give data about the level scheme. Direct and α-coincident γ-spectra have been measured using Ge(Li) and Si(Li) detectors, obtaining the characteristic electromagnetic transitions in ²³³Pa. Nine new γ-transitions are found, relative to the most recent compilation made by Ellis. In the level scheme, the existence of a level at 306.1 keV is confirmed. A level at 257.1 keV, previously suggested, is evidenced. The level at 300.5 keV is proposed as the $\text{7}\text{2}{}^{\mathrm{?}}$ component of the $\text{5}\text{2}\text{(523)}$ band, hence proposing the 306.1 keV level as the $\text{7}\text{2}{}^{\mathrm{+}}$ term of the $\text{5}\text{2}\text{(642)}$ band.     

Oxygenation of calixarene phenol rings

[structure: see text] The first examples of epoxy-p-quinol and diepoxy-p-quinol calixarene derivatives have been obtained by base-promoted direct addition of O(2)(oxygenation) to calixarene phenol rings. The regio- and stereochemistry of these derivatives was determined by 2D NMR studies, in conjunction with MM3 calculations, and X-ray crystallography. Both the oxygenation and the subsequent carbonyl reduction occur with a preferential attack to the less hindered exo face of the calixarene rings.     

Ancillary ligand effect on single-site styrene polymerization: isospecificity of group 4 metal bis(phenolate) catalysts

Styrene is polymerized isospecifically by group 4 metal complexes that contain a C2-symmetrically coordinated 1,4-dithiabutane-linked bis(phenolato) ligand activated by methylaluminoxane.     

Measurement of the resistivity of porous materials with an alternating air-flow method

Air-flow resistivity is a main parameter governing the acoustic behavior of porous materials for sound absorption. The international standard ISO 9053 specifies two different methods to measure the air-flow resistivity, namely a steady-state air-flow method and an alternating air-flow method. The latter is realized by the measurement of the sound pressure at 2 Hz in a small rigid volume closed partially by the test sample. This cavity is excited with a known volume-velocity sound source implemented often with a motor-driven piston oscillating with prescribed area and displacement magnitude. Measurements at 2 Hz require special instrumentation and care. The authors suggest an alternating air-flow method based on the ratio of sound pressures measured at frequencies higher than 2 Hz inside two cavities coupled through a conventional loudspeaker. The basic method showed that the imaginary part of the sound pressure ratio is useful for the evaluation of the air-flow resistance. Criteria are discussed about the choice of a frequency range suitable to perform simplified calculations with respect to the basic method. These criteria depend on the sample thickness, its nonacoustic parameters, and the measurement apparatus as well. The proposed measurement method was tested successfully with various types of acoustic materials.     

Continuous-wave mid-infrared frequency conversion in silicon nanowaveguides

We report the first demonstration of cw wavelength conversion from the telecommunications band to the mid-IR (MIR) region via four-wave mixing in silicon nanowaveguides. We measure a parametric bandwidth of 748 nm by converting a 1636 nm signal to produce a 2384 nm idler and show continuously tunable wavelength conversion from 1792 to 2116 nm. This report indicates that the advantages of silicon photonics may be leveraged to create devices for a large range of MIR applications that require cw operation.     

Spectral amplitude and phase measurement of ultrafast pulses using all-optical differential tomography

We demonstrate a simple, all-optical, fiber-based method for characterizing the spectral amplitude and phase of ultrafast pulses using a differential tomographic measurement realized via four-wave mixing. The technique is applied to subpicosecond pulses in the C-band of the telecommunication spectrum. Characterization of amplified pulses and propagation through dispersive media is demonstrated and compared with autocorrelation measurements and calculated predictions. We show how our approach can be extended to larger bandwidths in similar systems, extending tomographic reconstruction of coherent fields to nearly an octave of bandwidth while maintaining a robust, waveguide-based geometry.