Self-Supervised Variational Auto-Encoders

Density estimation, compression, and data generation are crucial tasks in artificial intelligence. Variational Auto-Encoders (VAEs) constitute a single framework to achieve these goals. Here, we present a novel class of generative models, called self-supervised Variational Auto-Encoder (selfVAE), which utilizes deterministic and discrete transformations of data. This class of models allows both conditional and unconditional sampling while simplifying the objective function. First, we use a single self-supervised transformation as a latent variable, where the transformation is either downscaling or edge detection. Next, we consider a hierarchical architecture, i.e., multiple transformations, and we show its benefits compared to the VAE. The flexibility of selfVAE in data reconstruction finds a particularly interesting use case in data compression tasks, where we can trade-off memory for better data quality and vice-versa. We present the performance of our approach on three benchmark image data (Cifar10, Imagenette64, and CelebA).     

Rhenium(I) and technetium(I) fac-M(NSO)(CO)3 (M = Re,Tc) tricarbonyl complexes,with a tridentate NSO bifunctional agent: Synthesis,structural characterization,and radiochemistry

The synthesis and structural characterization of the neutral rhenium complex fac-[Re(NSO)(CO)₃], Re-1, where (NSO) is a tridentate bifunctional chelating agent, 3-(carboxymethylthio)-3-(1H-imidazol-4-yl)propanoic acid (1), is presented. The complex crystallized from methanol–water and its structure was assigned by IR and ¹H, ¹³C NMR spectroscopies and X-ray crystallography. Furthermore, the analogous technetium complex fac-[^99mTc(NSO)(CO)₃], ^99mTc-1, was synthesized in high yield by reacting ligand 1 with the fac-[^99mTc(OH₂)₃(CO)₃]⁺ precursor for 30 min at 85 °C. The tracer complex was found to be more than 95% stable in the L-histidine challenge experiment. Our data indicate that the bifunctional NSO chelating agent 1 can be successfully applied for the development of potential ^99mTc-radiopharmaceuticals.     

The effect of physicochemical parameters on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange

The effect of physicochemical parameters such as pH, salinity (e.g. [NaCl]) and competitive cation (e.g. Ca²⁺ and Fe³⁺) concentration on the separation recovery of plutonium and uranium from aqueous solutions by cation exchange has been investigated. The investigation was performed to evaluate the applicability of cation exchange as separation and pre-concentration method prior to the radiometric analysis of uranium and plutonium isotopes in natural water samples. Application of the method to test solutions of constant radionuclide concentration and variable composition (0.1, 0.5 and 1 M NaCl; 0.1 and 0.5 M Ca(NO₃)₂; 0.1 and 1 mM FeCl₃; 10) has generally shown that: (1) the optimum pH is 4.5 for uranium and plutonium, (2) increasing salinity results in slightly lower for uranium and significantly higher chemical recovery plutonium and (3) the presence of Ca(II) cations doesn’t significantly affect the chemical recovery of both radionuclides. Contrary, the presence of Fe(III) cations ([Fe(III)] > 0.1 mM) results in significantly lower chemical recovery for both radionuclides (<50%). The later is attributed to the formation of Fe(III) colloids, which present increased chemical affinity for uranium and plutonium and hence compete with the radionuclide binding by the resin. Nevertheless, the results indicate that the method could be successfully applied to a wide range of natural waters.     

Direct determination of five fluoroquinolones in chicken whole blood and in veterinary drugs by HPLC

A direct, accurate, and sensitive chromatographic analytical method for the quantitative determination of five fluoroquinolones (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin) in chicken whole blood is proposed in the present study. For quantitative determination lamotrigine was used as internal standard at a concentration of 20 ng/microL. The developed method was successfully applied to the determination of enrofloxacin, as the main component of commercially available veterinary drugs. Fluoroquinolone antibiotics were separated on an Inertsil (250 x 4 mm) C8, 5 microm, analytical column, at ambient temperature. The mobile phase consisted of a mixture of citric acid (0.4 mol L(-1))-CH3OH-CH3CN (87:9:4% v/v) leading to retention times less than 14 min, at a flow rate 1.4 mL min(-1). UV detection at 275 nm provided limits of detection of 2 ng/mL per 20 microL injected volume for enoxacin, norfloxacin, and ciprofloxacin, 0.4 ng/mL for ofloxacin, and 4 ng/mL for enrofloxacin. Preparation of chicken blood samples is based on the deproteinization with acetonitrile while the pharmaceutical drug was simply diluted with water. Peaks of examined analytes in real samples were identified by means of a photodiode array detector. The method was validated in terms of within-day (n=6) precision and accuracy after chicken whole blood sample deproteinization by CH3CN. Using 50 microL of chicken blood sample, recovery rates at fortification levels of 40, 60, and 80 ng ranged from 86.7% to 103.7%. The applicability of the method was evaluated using real samples from chicken under fluoroquinolone treatment.     

Illustrating the power of singlet oxygen chemistry in a synthetic context: biomimetic syntheses of litseaverticillols A-G, I and J and the structural reassignment of litseaverticillol E

Biomimetic syntheses of the litseaverticillols A-G, I and J are reported herein. The syntheses rely heavily on the application of two different modes of reaction for photochemically generated singlet oxygen, namely, the [4+2] cycloaddition of singlet oxygen (1O2) with furans and the ene reaction of 1O2 with double bonds. The highlight of these syntheses is a one-pot cascade sequence, involving five synthetic operations initiated by a [4+2] reaction, to form the fully functionalised litseaverticillol core. A series of regioselective ene reactions are then used to appositely functionalise the side chains. The synthesis of litseaverticillol E (both its originally proposed and its actual structures) allows a structural reassignment of this natural product.     

Silver Nanoparticles Using Eucalyptus or Willow Extracts (AgNPs) as Contact Lens Hydrogel Components to Reduce the Risk of Microbial Infection

Eucalyptus leaves (ELE) and willow bark (WBE) extracts were utilized towards the formation of silver nanoparticles (AgNPs(ELE), AgNPs(WBE)). AgNPs(ELE) and AgNPs(WBE) were dispersed in polymer hydrogels to create pHEMA@AgNPs(ELE)_2 and pHEMA@AgNPs(WBE)_2 using hydroxyethyl-methacrylate (HEMA). The materials were characterized in a solid state by X-ray fluorescence (XRF) spectroscopy, X-ray powder diffraction analysis (XRPD), thermogravimetric differential thermal analysis (TG-DTA), differential scanning calorimetry (DTG/DSC) and attenuated total reflection spectroscopy (ATR-FTIR) and ultraviolet visible (UV-vis) spectroscopy in solution. The antimicrobial potential of the materials was investigated against the Gram-negative bacterial strain Pseudomonas aeruginosa (P. aeruginosa) and the Gram-positive bacterial strain of the genus Staphylococcus epidermidis (S. epidermidis) and Staphylococcus aureus (S. aureus), which are involved in microbial keratitis. The percentage of bacterial viability of P. aeruginosa and S. epidermidis upon their incubation over the pHEMA@AgNPs(ELE)_2 discs is interestingly low (28.3 and 6.8% respectively), while the inhibition zones (IZ) formed are 12.3 ± 1.7 and 13.2 ± 1.2 mm, respectively. No in vitro toxicity of this material towards human corneal epithelial cells (HCEC) was detected. Despite its low performance against S. aureus, pHEMA@AgNPs(ELE)_2 could be an efficient candidate towards the development of contact lenses that reduces microbial infection risk.     

Nanostructure vs. microstructure: Morphological and thermomechanical characterization of poly(l-lactic acid)/layered silicate hybrids

Nano- and micro-composites of poly(l-lactic acid) (PLLA) with various loadings of natural and hexadecylamine-modified montmorillonite were prepared by the solvent casting method to study the effect of nanostructure on the thermomechanical properties of the hybrid materials. The changes on structure and surface of montmorillonite, induced by the ion-exchange modification process, were characterized by X-ray diffraction (XRD) analysis and zeta-potential determination, while the morphology of the hybrids and the dispersion of the clay into the polymer matrix were examined by XRD, transmission electron microscopy and atomic force microscopy. The results showed that, although at low clay content exfoliation dominates, for filler loadings greater than 5 wt% both exfoliation and intercalation of the clay filler are observed. Thermal degradation studies of the materials produced using thermogravimetry revealed the introduction of a small amount of organo-modified silicate significantly improves their thermal stability. Differential scanning calorimetry showed the thermal behavior of the polymer matrix strongly depends on the nature and content of the silicate filler. Scanning electron microscopy of the deformed surfaces affirmed a different deformation process mechanism between the two types of composites.     

Allosteric Inhibition of the SARS-CoV-2 Main Protease: Insights from Mass Spectrometry Based Assays**

The SARS-CoV-2 main protease (M^pro) cleaves along the two viral polypeptides to release non-structural proteins required for viral replication. M^Pro is an attractive target for antiviral therapies to combat the coronavirus-2019 disease. Here, we used native mass spectrometry to characterize the functional unit of M^pro. Analysis of the monomer/dimer equilibria reveals a dissociation constant of K_d=0.14±0.03 μM, indicating M^Pro has a strong preference to dimerize in solution. We characterized substrate turnover rates by following temporal changes in the enzyme-substrate complexes, and screened small molecules, that bind distant from the active site, for their ability to modulate activity. These compounds, including one proposed to disrupt the dimer, slow the rate of substrate processing by ≈35 %. This information, together with analysis of the x-ray crystal structures, provides a starting point for the development of more potent molecules that allosterically regulate M^Pro activity.     

General convergence conditions of Newton’s method for m-Fréchet differentiable operators

We present a local as well as a semilocal convergence analysis for Newton’s method for approximating a locally unique solution of a nonlinear equation in a Banach space setting. Our hypotheses involve m-Fréchet-differentiable operators and general Lipschitz-type hypotheses, where m≥2 is a positive integer. The new convergence analysis unifies earlier results; it is more flexible and provides a finer convergence analysis than in earlier studies such as Argyros in J. Comput. Appl. Math. 131:149–159, 2001, Argyros and Hilout in J. Appl. Math. Comput. 29:391–400, 2009, Argyros and Hilout in J. Complex. 28:364–387, 2012, Argyros et al. Numerical Methods for Equations and Its Applications, CRC Press/Taylor & Francis, New York, 2012, Gutiérrez in J. Comput. Appl. Math. 79:131–145, 1997, Ren and Argyros in Appl. Math. Comput. 217:612–621, 2010, Traub and Wozniakowski in J. Assoc. Comput. Mech. 26:250–258, 1979. Numerical examples are presented further validating the theoretical results.