Tetrachlorobisphenol-A adipate polymers. III. Synthesis and crystalline properties of block copolymers of poly(tetrachlorobisphenol-A adipate) and polystyrene

Block copolymers having poly(tetrachlorobisphenol-A adipate) (PTBA) and polystyrene (PS) sequences were synthesized were synthesized by photodegradation of an oxime-containing polyester in the presence of styrene. Crystallinity, melting behavior, and spherulitic growth rates were studied as a function of block compositions and molecular weights. A model was proposed based on a complete phase separation between the two components. The influence of the polymer composition on the spherulitic growth rate is described by introducing a supplementary pre-exponential factor into the equation for the growth rate. This parameter is a measure of the tortuosity of the actual path that has to be covered owing to the presence of the noncrystallizable blocks.     

Elementary excitations of quantum critical (2+1)-dimensional antiferromagnets

It has been proposed that there are degrees of freedom intrinsic to quantum critical points that can contribute to quantum critical physics. We point out that this conclusion is quite general below the upper critical dimension. We show that in (2+1)D antiferromagnets Skyrmion excitations are stable at criticality and identify them as the critical excitations. We find exact solutions composed of Skyrmion and anti-Skyrmion superpositions, which we call topolons. We include the topolons in the partition function and renormalize by integrating out small size topolons and short wavelength spin waves. We obtain a correlation length exponent nu=0.690 666 and anomalous dimension eta=0.0166.     

Enhancement of two-photon absorption cross-section and singlet-oxygen generation in porphyrins upon beta-functionalization with donor-acceptor substituents

The microwave-enhanced synthesis, comparative singlet oxygen sensitization efficiency, and nonlinear optical characterization of a new beta-functionalized porphyrin and its copper complex are described. We show that the introduction of a donor-acceptor push-pull conjugated fragment in the beta position strongly perturbs the porphyrin electronic structure leading to a remarkable one- and two-photon NIR absorption enhancement.     

Personalized Metabolic Profile by Synergic Use of NMR and HRMS

A new strategy that takes advantage of the synergism between NMR and UHPLC–HRMS yields accurate concentrations of a high number of compounds in biofluids to delineate a personalized metabolic profile (SYNHMET). Metabolite identification and quantification by this method result in a higher accuracy compared to the use of the two techniques separately, even in urine, one of the most challenging biofluids to characterize due to its complexity and variability. We quantified a total of 165 metabolites in the urine of healthy subjects, patients with chronic cystitis, and patients with bladder cancer, with a minimum number of missing values. This result was achieved without the use of analytical standards and calibration curves. A patient’s personalized profile can be mapped out from the final dataset’s concentrations by comparing them with known normal ranges. This detailed picture has potential applications in clinical practice to monitor a patient’s health status and disease progression.     

Correlation between carbon nanotube microstructure and their catalytic efficiency towards the p-coumaric acid degradation

Pristine and annealed multi-walled C nanotubes are preliminarily tested as catalysts towards the degradation of p-coumaric acid with better performances than the widely used activated carbon. In order to clarify the origin of their different catalytic efficiency, the samples are analysed by means of high-resolution transmission electron microscopy, X-ray photoemission, reflection electron energy loss and micro-Raman spectroscopy. Chemical composition, mass density, bonding configurations and threefold- to fourfold-coordinated carbon bonding ratios are determined. The comparative discussion of the results obtained leads to attribute the higher catalytic activity of the pristine nanotubes to their larger sp²/sp³ carbon bonding fraction and greater amount of oxygen containing functional groups.     

Identification and Directed Development of Non‐Organic Catalysts with Apparent Pan‐Enzymatic Mimicry into Nanozymes for Efficient Prodrug Conversion

Nanozymes, nanoparticles that mimic the natural activity of enzymes, are intriguing academically and are important in the context of the Origin of Life. However, current nanozymes offer mimicry of a narrow range of mammalian enzymes, near‐exclusively performing redox reactions. We present an unexpected discovery of non‐proteinaceous enzymes based on metals, metal oxides, 1D/2D‐materials, and non‐metallic nanomaterials. The specific novelty of these findings lies in the identification of nanozymes with apparent mimicry of diverse mammalian enzymes, including unique pan‐glycosidases. Further novelty lies in the identification of the substrate scope for the lead candidates, specifically in the context of bioconversion of glucuronides, that is, human metabolites and privileged prodrugs in the field of enzyme‐prodrug therapies. Lastly, nanozymes are employed for conversion of glucuronide prodrugs into marketed anti‐inflammatory and antibacterial agents, as well as “nanozyme prodrug therapy” to mediate antibacterial measures.     

Rapid separation of post‐blast explosive residues on glass electrophoresis microchips

This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C⁴D) for the separation and detection of inorganic anions in post‐blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C⁴D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 V_pp. The separation of Cl^?, NO₃^?, NO₂^?, SO₄^2?, ClO₄^? and ClO₃^? was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 10⁴ and 1.7 × 10⁵ plates/m. The found limits of detection ranged between 2.5 and 9.5 μmol/L. Last, real samples of post‐blast explosive residues were analyzed on the ME‐C⁴D devices obtaining successfully the determination of Cl^?, NO₃^? and SO₄^2?. The achieved concentration values varied between 12.8–72.5 mg/L for Cl^?, 1.7–293.1 mg/L for NO₃^? and 1.3–201.3 mg/L for SO₄^2?. The data obtained using ME‐C⁴D devices were in good agreement with the concentrations found by ion chromatography. The approach reported herein has provided short analysis time, instrumental simplicity, good analytical performance and low cost. Furthermore, the ME‐C⁴D devices emerge as a powerful and portable analytical platform for on‐site analysis demonstrating to be a promising tool for the crime scene investigation.     

A semi-analytical finite element formulation for modeling stress wave propagation in axisymmetric damped waveguides

A semi-analytical finite element (SAFE) method is presented for analyzing the wave propagation in viscoelastic axisymmetric waveguides. The approach extends a recent study presented by the authors, in which the general SAFE method was extended to account for material damping. The formulation presented in this paper uses the cylindrical coordinates to reduce the finite element discretization over the waveguide cross-section to a mono-dimensional mesh. The algorithm is validated by comparing the dispersion results with viscoelastic cases for which a Superposition of Partial Bulk Waves solution is known. The formulation accurately predicts dispersion properties and does not show any missing root. Applications to viscoelastic axisymmetric waveguides with varying mechanical and geometrical properties are presented.     

A novel method for quantification of the folding of elastic laminae in elastic arteries

A transgenic mouse overexpressing the human form of semicarbazide-sensitive amine oxidase (SSAO) is known to have an abnormal structure of the elastic laminae and the elastic fibres in the aorta. Compared to the non-transgenic littermates, the elastic laminae are less folded. In order to quantify the undulation of this structure, an image analysis program that identified the elastic laminae was developed. The program measures the area fraction in different sectors from a plane parallel to the aorta wall. Images were taken from unstained aorta specimens where the elastic laminae were visualised with phase contrast microscopy. A contextual operation of the images produced a local orientation estimation for every linear structure. The image was then thresholded in eight sectors from 0 degrees to 180 degrees , with different orientation angles. The results show that the area fraction of the elastic laminae was significantly lower for the transgenic mouse in all sectors measured except for two. At 0-25 degrees , no difference was seen. In the sector at 160-180 degrees , parallel to the aorta wall, the area fraction of elastic laminae was instead significantly higher in the transgenic mouse. A novel method is presented, developed for detection and quantification of pathological changes in the elastic laminae in the aorta wall. The method gave reliable results and is considered to be a useful tool for morphometric studies of aorta with this kind of altered morphology concerning the elastic laminae. When compared with tangent count, the control group had a significantly larger mean curvature.