Thermodynamic and Dynamic Transitions and Interaction Aspects in Reorientation Dynamics of Molecular Probe in Organic Compounds: A Series of 1-alkanols with TEMPO.

The spectral and dynamic properties of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) in a series of 1-alkanols ranging from methanol to 1-decanol over a temperature range 100-300 K were investigated by electron spin resonance (ESR). The main characteristic ESR temperatures connected with slow to fast motion regime transition; T50G 's and TX1fast 's are situated above the corresponding glass temperatures, Tg, and for the shorter members, the T50G 's lie above or close to melting point, Tm, while the longer ones the T50G < Tm relationship indicates that the TEMPO molecules are in the local disordered regions of the crystalline media. The T50G 's and especially TX1fast 's are compared with the dynamic crossover temperatures, TXVISC = 8.72M0.66, as obtained by fitting the viscosity data in the liquid n-alkanols with the empirical power law. In particular, for NC > 6, the TX1fast 's lie rather close to the TXVISC resembling apolar n-alkanes [PCCP 2018,20,11145-11151], while for NC < 6, they are situated in the vicinity of Tm. The absence of a coincidence for lower1-alkanols indicates that the T50G is significantly influenced by the mutual interaction between the polar TEMPO and the protic polar medium due to the increased polarity and proticity destroyed by the larger-scale melting transition.

Thermal expansion of free volume in "classic" and regulated dimethacrylates: photocured directly and via a mask to study pillar formation.

The temperature dependence of free volume in dimethacrylates (poly2M), cured by direct irradiation (poly2M-A) or via a mask (poly2M-B), and in a thiol-based 2M sample (poly2M-co-EDDT), was investigated by positron annihilation lifetime spectroscopy (PALS) and dilatometry (DIL) to study the influence of thiol regulation on the microstructure via free volume characteristics. It was found that the free volume fraction as determined from experimental data by using the standard spherical approach for the hole shapes showed systematic differences from the analogous quantity as evaluated from the lattice-hole theory. Much better results were obtained for cylindrical holes, which expand 'anisotropically' in poly2M samples and 'isotropically' in the poly2M-co-EDDT resin. In addition, the hydrogen bond changes and the conversion of monomers in cured samples studied by near infra-red spectroscopy (NIR) revealed spectrum-structure correlations for the final cured thermosets.

An elevated concentration of MoS2 lowers the efficacy of liquid-phase exfoliation and triggers the production of MoOx nanoparticles.

It is generally accepted that liquid-phase exfoliation (LPE) enables large-scale production of few-layer MoS2 flakes. In our work, we studied in detail few-layer MoS2 oxidation in the course of standard LPE in a water/ethanol solution. We demonstrate that an increase of the initial MoS2 concentration above a certain threshold triggers a pronounced oxidation and the exfoliation process starts to produce MoOx nanoparticles. A subsequent decrease of the water pH along with an increased content of SO42- suggests an oxidation scenario of few-layer MoS2 oxidation towards MoOx nanoparticles. Moreover, the lowered pH leads to agglomeration and sedimentation of the few-layer MoS2 flakes, which significantly lowers their production yield. We employed a large number of physico-chemical techniques to study the MoS2-to-MoOx transformation and found a threshold value of 10 mg ml-1 of the initial MoS2 concentration to trigger this transformation.

Products of Selenite/Thiols Interaction Have Reducing Properties, Cleave Plasmid DNA and Decrease Rat Blood Pressure and Tension of Rat Mesenteric Artery.

Selenium compounds exert their antioxidant activity mostly when the selenium atom is incorporated into selenoproteins. In our work, we tested the possibility that selenite itself interacts with thiols to form active species that have reducing properties. Therefore, we studied the reduction of 2-(4-carboxyphenyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazol-1-yloxy-3-oxide radical (•cPTIO), damage of plasmid DNA (pDNA), modulation of rat hemodynamic parameters and tension of isolated arteries induced by products of interaction of selenite with thiols. We found that the products of selenite interaction with thiols had significant reducing properties that could be attributed mainly to the selenide and that selenite had catalytic properties in the access of thiols. The potency of thiols to reduce •cPTIO in the interaction with selenite was cysteine > homocysteine > glutathione reduced > N-acetylcysteine. Thiol/selenite products cleaved pDNA, with superoxide dismutase enhancing these effects suggesting a positive involvement of superoxide anion in the process. The observed •cPTIO reduction and pDNA cleavage were significantly lower when selenomethionine was used instead of selenite. The products of glutathione/selenite interaction affected several hemodynamic parameters including rat blood pressure decrease. Notably, the products relaxed isolated mesenteric artery, which may explain the observed decrease in rat blood pressure. In conclusion, we found that the thiol/selenite interaction products exhibited significant reducing properties which can be used in further studies of the treatment of pathological conditions caused by oxidative stress. The results of decreased rat blood pressure and the tension of mesenteric artery may be perspective in studies focused on cardiovascular disease and their prevention.

Selective Tumor Hypoxia Targeting Using M75 Antibody Conjugated Photothermally Active MoOx Nanoparticles.

Photothermal therapy (PTT) mediated at the nanoscale has a unique advantage over currently used cancer treatments, by being spatially highly specific and minimally invasive. Although PTT combats traditional tumor treatment approaches, its clinical implementation has not yet been successful. The reasons for its disadvantage include an insufficient treatment efficiency or low tumor accumulation. Here, we present a promising new PTT platform combining a recently emerged two-dimensional (2D) inorganic nanomaterial, MoOx, and a tumor hypoxia targeting element, the monoclonal antibody M75. M75 specifically binds to carbonic anhydrase IX (CAIX), a hypoxia marker associated with many solid tumors with a poor prognosis. The as-prepared nanoconjugates showed highly specific binding to cancer cells expressing CAIX while being able to produce significant photothermal yield after irradiation with near-IR wavelengths. Small aminophosphonic acid linkers were recognized to be more effective over the combination of poly(ethylene glycol) chain and biotin-avidin-biotin bridge in constructing a PTT platform with high tumor-binding efficacy. The in vitro cellular uptake of nanoconjugates was visualized by high-resolution fluorescence microscopy and label-free live cell confocal Raman microscopy. The key to effective cancer treatment may be the synergistic employment of active targeting and noninvasive, tumor-selective therapeutic approaches, such as nanoscale-mediated PTT. The use of active targeting can streamline nanoparticle delivery increasing photothermal yield and therapeutic success.

A Combined Atomic and Molecular Probe Characterization of Aromatic Hydrocarbons via PALS and ESR: Methylbenzene.

A combined study of one of the simplest aromatic hydrocarbons, i.e., methylbenzene (toluene) (TOL), via the annihilation of an ortho-positronium (o-Ps) probe via positron annihilation lifetime spectroscopy (PALS) and the rotation dynamics of nitroxide spin probe 2,2,6,6-tetramethyl-piperidinyl-1-oxy (TEMPO) using electron spin resonance (ESR) over a wide temperature range, 10-300 K, is reported. The o-Ps lifetime, τ3, and the relative o-Ps intensity, I3, as a function of temperature exhibit changes defining several characteristic PALS temperatures in the slowly and rapidly cooled samples. Similarly, the spectral parameter of TEMPO mobility in TOL, 2Azz', and its correlation time, τc, reveal several effects at a set of the characteristic ESR temperatures, which were determined and compared with the PALS results. Finally, the physical origins of the changes in free volume expansion and spin probe mobility are revealed. They are reflected in a series of the mutual coincidences between the characteristic PALS and ESR temperatures and appropriate complementary thermodynamic and dynamic techniques.

Biosensor Based on Peroxidase-Mimetic Nanozyme and Lactate Oxidase for Accurate L-Lactate Analysis in Beverages.

Precision analysis of the key biological metabolites such as L-lactate has great practical importance for many technological processes in food technology, including beverage production. Here we describe a new, highly selective, and sensitive biosensor for accurate L-lactate assay based on a combination of peroxidase-mimetic nanozymes with microbial lactate oxidase (LOx) immobilized onto the surface of a graphite-rod electrode (GE). The peroxidase-like nanozymes were synthesized using the debris of carbon microfibers (CFs) functionalized with hemin (H) and modified with gold nanoparticles (AuNPs) or platinum microparticles (PtMPs). The nanozyme formed with PtMPs as well as corresponding bioelectrodes based on it (LOx-CF-H-PtMPs/GE) is characterized by preferable catalytic and operational characteristics, so it was selected for the analysis of L-lactate content in real samples of grape must and red wine. The results of the L-lactate analysis obtained by the developed biosensors are highly correlated with a very selective spectrophotometric approach used as a reference. The developed biosensor, due to its high selectivity and sensitivity, is very prospective not only for the beverage industry and food technology, but also for clinical diagnostics and medicine, as well as in other applications where the accurate analysis of L-lactate is highly important.

UV-Cured Green Polymers for Biosensorics: Correlation of Operational Parameters of Highly Sensitive Biosensors with Nano-Volumes and Adsorption Properties.

The investigated polymeric matrixes consisted of epoxidized linseed oil (ELO), acrylated epoxidized soybean oil (AESO), trimethylolpropane triglycidyl ether (RD1), vanillin dimethacrylate (VDM), triarylsulfonium hexafluorophosphate salts (PI), and 2,2-dimethoxy-2-phenylacetophenone (DMPA). Linseed oil-based (ELO/PI, ELO/10RD1/PI) and soybean oil-based (AESO/VDM, AESO/VDM/DMPA) polymers were obtained by cationic and radical photopolymerization reactions, respectively. In order to improve the cross-linking density of the resulting polymers, 10 mol.% of RD1 was used as a reactive diluent in the cationic photopolymerization of ELO. In parallel, VDM was used as a plasticizer in AESO radical photopolymerization reactions. Positron annihilation lifetime spectroscopy (PALS) was used to characterize vegetable oil-based UV-cured polymers regarding their structural stability in a wide range of temperatures (120-320 K) and humidity. The polymers were used as laccase immobilization matrixes for the construction of amperometric biosensors. A direct dependence of the main operational parameters of the biosensors and microscopical characteristics of polymer matrixes (mostly on the size of free volumes and water content) was established. The biosensors are intended for the detection of trace water pollution with xenobiotics, carcinogenic substances with a very negative impact on human health. These findings will allow better predictions for novel polymers as immobilization matrixes for biosensing or biotechnology applications.

On the Mutual Relationships between Molecular Probe Mobility and Free Volume and Polymer Dynamics in Organic Glass Formers: cis-1,4-poly(isoprene).

We report on the reorientation dynamics of small spin probe 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) in cis-1,4-poly(isoprene) (cis-1,4-PIP10k) from electron spin resonance (ESR) and the free volume of cis-1,4-PIP10k from positron annihilation lifetime spectroscopy (PALS) in relation to the high-frequency relaxations of cis-1,4-PIP10k using light scattering (LS) as well as to the slow and fast processes from broadband dielectric spectroscopy (BDS) and neutron scattering (NS). The hyperfine coupling constant, 2Azz '(T), and the correlation times, τ c(T), of cis-1,4-PIP10k/TEMPO system as a function of temperature exhibit several regions of the distinct spin probe TEMPO dynamics over a wide temperature range from 100 K up to 350 K. The characteristic ESR temperatures of changes in the spin probe dynamics in cis-1,4-PIP10k/TEMPO system are closely related to the characteristic PALS ones reflecting changes in the free volume expansion from PALS measurement. Finally, the time scales of the slow and fast dynamics of TEMPO in cis-1,4-PIP10k are compared with all of the six known slow and fast relaxation modes from BDS, LS and NS techniques with the aim to discuss the controlling factors of the spin probe reorientation mobility in polymer, oligomer and small molecular organic glass-formers.

The Potential Application of Magnetic Nanoparticles for Liver Fibrosis Theranostics.

Liver fibrosis is a major cause of morbidity and mortality worldwide due to chronic liver damage and leading to cirrhosis, liver cancer, and liver failure. To date, there is no effective and specific therapy for patients with hepatic fibrosis. As a result of their various advantages such as biocompatibility, imaging contrast ability, improved tissue penetration, and superparamagnetic properties, magnetic nanoparticles have a great potential for diagnosis and therapy in various liver diseases including fibrosis. In this review, we focus on the molecular mechanisms and important factors for hepatic fibrosis and on potential magnetic nanoparticles-based therapeutics. New strategies for the diagnosis of liver fibrosis are also discussed, with a summary of the challenges and perspectives in the translational application of magnetic nanoparticles from bench to bedside.

Molecular probe dynamics and free volume heterogeneities in n-propanol confined in a regular MCM-41 matrix by ESR and PALS.

A combined investigation of the spin probe TEMPO mobility and the free volume holes in n-propanol (n-PrOH) confined in a regular virgin MCM-41 matrix by means of ESR or PALS techniques, respectively, is reported. Dynamics of spin probe TEMPO alters at several characteristic ESR temperatures which are close to the characteristic PALS ones reflecting the changes in o-Ps annihilation and the related free volume. Correlations between these characteristic ESR and PALS temperatures indicate the common physical origins of the respective changes in the free volume expansion and the TEMPO mobility in the confined liquid n-PrOH. The significant difference in dynamic heterogeneity of TEMPO after confinement and free volume dispersion reflect the strongly altered structural-dynamic relationships in the confined n-PrOH medium with respect to the bulk situation.

Dynamics of Confined Short-Chain alkanol in MCM-41 by Dielectric Spectroscopy: Effects of matrix and system Treatments and Filling Factor.

The dynamics of n-propanol confined in regular MCM-41 matrix with the pore size Dpore = 40 Å, under various matrix conditioning and sample confining conditions, using broadband dielectric spectroscopy (BDS), is reported. First, various drying procedures with the capacitor filling under air or N2 influence the BDS spectra of the empty MCM-41 and the confined n-PrOH/MCM-41 systems, but have a little effect on the maximum relaxation time of the main process. Finally, various filling factors of n-PrOH medium in the optimally treated MCM-41 system lead to unimodal or bimodal spectra interpreted in terms of the two distinct dynamic phases in the confined states.

Simple and Eco-Friendly Route from Agro-Food Waste to Water Pollutants Removal.

The current study reflects the demand to mitigate the environmental issues caused by the waste from the agriculture and food industry. The crops that do not meet the supply chain requirements and waste from their processing are overfilling landfills. The mentioned wastes contain cellulose, which is the most abundant carbon precursor. Therefore, one of the possibilities of returning such waste into the life cycle could be preparing the activated carbon through an eco-friendly and simple route. Herein, the carrot pulp from the waste was used. Techniques such as thermogravimetric analysis (TGA), elemental analysis (EA), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and x-ray diffraction (XRD) were used to investigate the thermal treatment effect during the carbon material preparation. The development of microstructure, phase formation, and chemical composition of prepared material was evaluated. The obtained carbon material was finally tested for water cleaning from a synthetic pollutant such as rhodamine B and phloxine B. An adsorption mechanism was proposed on the base of positron annihilation lifetime spectroscopy (PALS) results and attributed to the responsible interactions. It was shown that a significant carbon sorbent from the organic waste for water purification was obtained.

Correction: Gamma ray assisted modification of carbon quantum dot/polyurethane nanocomposites: structural, mechanical and photocatalytic study.

[This corrects the article DOI: 10.1039/C9RA00500E.].

Microstructural study of epoxy-based thermosets prepared by "classical" and cationic frontal polymerization.

A microstructural study of bisphenol-A diglycidyl ether (BADGE), prepared via both "classical" and novel photo- and thermally-induced cationic frontal polymerization, can help to understand the relationships between the microstructure of epoxides and their material properties, as well as the propagation of frontal polymerization waves. Microstructural PALS characteristics, such as the ortho-positronium lifetime (τ o-Ps), lifetime distribution, and void fraction, were investigated in relation to the extension of H bonds obtained from ATR/FTIR and the bulk density. The thermal profiles of differently-induced RICFP revealed that photo-triggered propagation is twice as fast as thermally-induced RICFP, with a comparable maximal reaction temperature (∼283 °C) and heat conductivity. Both RICFP-based samples, induced by UV light and heat, showed a lower τ o-Ps, narrower lifetime distributions, and a reduced void fraction, in comparison to the "classical" cured anhydride-based epoxy sample. These may be the main factors which result in better material properties. In addition, both their radial and angular profiles of free volume fraction confirmed experimentally the rotational movement of the propagating frontal waves and their influence on the microstructural inhomogeneities, and the final material properties.

Microporous carbon fibers as electroconductive immobilization matrixes: Effect of their structure on operational parameters of laccase-based amperometric biosensor.

In this study, we describe the fabrication of sensitive biosensor for the detection of phenolic substrates using laccase immobilized onto two types of microporous carbon fibers (CFs). The main characteristics of microporous CFs used for preparation of biosensors are given. Two CFs were characterized by different specific surface area, CFA (<1 m2·g-1) and CFB (1448 m2·g-1), but with comparable size of the micropores estimated by positron annihilation lifetime spectroscopy. The structural analysis was shown that CFA is formed by thin interwoven fibers forming a highly porous structure, as well as CFB - by granular formations with uneven edges that shape a cellulose membrane of lower porosity. The results of amperometric analysis revealed that the laccase-bound CFs possesses better electrochemical behavior for laccase than non-modified rod carbon electrodes (control). Using chronoamperometric analysis, the operational parameters of the CFs-modified bioelectrodes were compared to control bioelectrodes. The bioelectrodes based on CFs have demonstrated 2.4-2.7 folds enhanced maximal current at substrate saturation (Imax) values, 1.2-1.4 folds increased sensitivity and twice wide linearity compared with control bioelectrodes. The sensitivity of the developed CFs-based bioelectrodes was improved compared with the laccase-bound electrodes, described in literature. The developed biosensor was tested for catechol analysis in the real communal wastewater sample.

Microstructural free volume and dynamics of cryoprotective DMSO-water mixtures at low DMSO concentration.

This work investigates the free-volume properties of the dimethyl sulfoxide (DMSO)-water mixtures by positron annihilation lifetime spectroscopy over a wide temperature range of 20-320 K. The processes of melting and solidification of the water, DMSO and the DMSO-water mixtures at 1.8, 2.0 and 10% vol. DMSO respectively were studied. It was found that the recrystallization during heating of the water-DMSO cryoprotective mixtures above 160 K at low DMSO concentrations is affected by the amount of DMSO in the mixture. The amount of amorphous phase formed during cooling influences the hysteresis between cooling and heating cycles which could be crucial for cell survival. Experiments also show the time dependence of crystallization which indicates that rapid heating can suppress this secondary crystallization which is undesirable during the cell thawing process. Similar concentrations of DMSO (1.8% and 2% vol. DMSO in water) where a 2% vol. DMSO mixture secures cell survival but 1.8 vol% does not, showed differences in structural and dynamic properties that are key factors in cell survival. These results were supported by differential scanning calorimetry and low frequency dielectric spectroscopy measurements. The obtained data are in strong agreement with the observed cryoprotective efficacy of the DMSO-water mixtures on living cells.

Antibacterial photodynamic activity of carbon quantum dots/polydimethylsiloxane nanocomposites against Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae.

Despite great efforts, the design of antibacterial surfaces is still a challenge. In this work, results of structural, mechanical, cytotoxic and antibacterial activities of hydrophobic carbon quantum dots/polydimethylsiloxane surfaces are presented. Antibacterial action of this surface is based on the generation of reactive oxygen species which cause bacteria damage by oxidative stress. At the same time, this surface was not cytotoxic towards the NIH/3T3 cells. Swelling-encapsulation-shrink method is applied for encapsulation of hydrophobic carbon quantum dots in medical grade silicone-polydimethylsiloxane. XPS and photoluminescence spectroscopy analyses confirm that hydrophobic carbon quantum dots have been encapsulated successfully into polydimethylsiloxane polymer matrix. Based on stress-strain test the improvement of mechanical properties of these nanocomposites is established. It is shown by electron paramagnetic resonance spectroscopy and luminescence method that nanocomposite generates singlet oxygen initiated by 470 nm blue light irradiation. Antibacterial testing shows the nanocomposite in the form of foil kills Staphylococcus aureus, Escherichia coli and Klebsiella pneumoniae and is very effective after only a 15 min irradiation.

Gamma ray assisted modification of carbon quantum dot/polyurethane nanocomposites: structural, mechanical and photocatalytic study.

In recent years, water pollution and contamination had become a major threat to the ecosystem. However, the use of nanostructured materials has been proven as a very promising approach in the treatment of polluted water. The present study reports the results of the gamma ray-assisted modification of hydrophobic carbon quantum dot (hCQD)/polyurethane nanocomposites for photocatalytic degradation of organic dyes. Different characterization methods were applied to investigate the influence of the different doses of gamma irradiation (1, 10 and 200 kGy) on the physical and chemical properties of nanocomposites (morphology, chemical content, mechanical properties, wettability, and potential for singlet oxygen generation). Surface morphology and mechanical properties analyses showed that gamma rays induced insignificant changes in the structure of nanocomposites, but the potential for singlet oxygen generation increased significantly. Here we also explore, in detail, the photocatalytic properties of gamma-ray modified hCQDs/polyurethane nanocomposites. UV-vis analysis showed that the removal efficiency of the rose bengal dye reached up to 97% for the nanocomposite irradiated with the dose of 200 kGy.

In situ investigation of the kinetics and microstructure during photopolymerization by positron annihilation technique and NIR-photorheology.

The microstructural free volume evolution during a photopolymerization process was studied on a commercial photopolymer (SPOT LV) in situ by positron annihilation lifetime spectroscopy (PALS) and concomitant NIR-photorheology. Analysis of the positron lifetime spectra revealed a high sensitivity of the PALS technique to the different phases of photopolymerization associated with different reaction rates as well as to the evolution of microstructural free-volume shrinkage, which was described at the molecular level by the Kohlrausch-Williams-Watts equation. The in situ PALS study of microstructural changes in photopolymerization was related to the vitrification (gel point) accompanied by shrinkage stress registered via NIR-photorheology. The simultaneous NIR measurements yield information on the monomer conversion of SPOT LV, which can be correlated to the occurrence of the gel point and the evolution of the microstructural free volume. This combined study allows us to see deeper into the crosslinking process and its influence on the resulting material characteristics.