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.

Regulation of Conjugate Rigid Plane Structure to Achieving Transformation of Fluorescent Recognition Properties

Bisbenzimidazole is an important class of fluorescence molecular probe materials with environmental, clinical and biological systems. Meanwhile, different bisbenzimidazole derivatives due to excellent coordination property and various fluorescence characteristic, were...

Molecular diffusion in ternary poly(vinyl alcohol) solutions

The diffusion kinetics of a molecular probe—rhodamine B—in ternary aqueous solutions containing poly(vinyl alcohol), glycerol, and surfactants was investigated using fluorescence correlation spectroscopy and dynamic light scattering. We show that the diffusion characteristics of rhodamine B in such complex systems is determined by a synergistic effect of molecular crowding and intermolecular interactions between chemical species. The presence of glycerol has no noticeable impact on rhodamine B diffusion at low concentration, but significantly slows down the diffusion of rhodamine B above 3.9% (w/v) due to a dominating steric inhibition effect. Furthermore, introducing surfactants (cationic/nonionic/anionic) to the system results in a decreased diffusion coefficient of the molecular probe. In solutions containing nonionic surfactant, this can be explained by an increased crowding effect. For ternary poly(vinyl alcohol) solutions containing cationic or anionic surfactant, surfactant—polymer and surfactant—rhodamine B interactions alongside the crowding effect of the molecules slow down the overall diffusivity of rhodamine B. The results advance our insight of molecular migration in a broad range of industrial complex formulations that incorporate multiple compounds, and highlight the importance of selecting the appropriate additives and surfactants in formulated products.

Spermine and Spermidine Detection through Restricted Intramolecular Rotations in a Tetraphenylethylene Derivative

Biogenic polyamines, especially spermine and spermidine, are associated with cell growth and development. These amines can be found at high concentrations in the tumor cells, tissues, and urine of cancer patients. In contrast, spermidine levels drop with age, and a possible connection between low endogenous spermidine concentrations and age-related deterioration has been suggested. Thus, the quantification of these amines in body fluids like urine could be used in the diagnosis of different pathological situations. Here a new fluorescent molecular probe based on a tetraphenylethylene derivative is reported. This probe is able to selectively detect these amines through the enhancement of the fluorescence emission of the resulting complex. This fluorescence enhancement may be related to restricted intramolecular rotations of TPE phenyl rings induced by the analyte. Theoretical studies were carried out to shed light on the observed selectivity. Finally, the detection of these amines in urine was performed with limits of detection of 0.70 µM and 1.17 µM for spermine and spermidine, respectively.

Synergistic Properties of Arabinogalactan (AG) and Hyaluronic Acid (HA) Sodium Salt Mixtures

The properties of mixtures of two polysaccharides, arabinogalactan (AG) and hyaluronic acid (HA), were investigated in solution by the measurement of diffusion coefficients D of water protons by DOSY (Diffusion Ordered SpectroscopY), by the determination of viscosity and by the investigation of the affinity of a small molecule molecular probe versus AG/HA mixtures in the presence of bovine submaxillary mucin (BSM) by 1HNMR spectroscopy. Enhanced mucoadhesive properties, decreased mobility of water and decreased viscosity were observed at the increase of AG/HA ratio and of total concentration of AG. This unusual combination of properties can lead to more effective and long-lasting hydration of certain tissues (inflamed skin, dry eye corneal surface, etc.) and can be useful in the preparation of new formulations of cosmetics and of drug release systems, with the advantage of reducing the viscosity of the solutions.

PHYSICAL AGING OF ORGANO-INORGANIC NANOCOMPOSITES BASED ON POLYIMIDE WITH CARD SUBSTITUENTS

The physical aging was investigated of obtained by sol-gel technology nanocomposites based on polyimide (PI) with card substituents and tetraethoxysylane (TEOS). The results for organic-inorganic composites, that contain of 5%. 20% or 50 % of TEOS, demonstrate that at temperatures well below (400K) the glass transition temperature of the polymer can take place changes in the dynamic characteristics of polymer macrochains and its permeability to low molecular probe as well as changes in aggregation of inorganic component. According to the methods of EPR, optical microscopy, etc. changes that occur in the characteristics of sol-gel polyimide based nanocomposites during long-term storage at temperatures much lower than the glass transition temperature of the polymer can be described as follows. The segmental mobility of the organic component is significantly reduced and the dynamic heterogeneity of the polymer increases. The decrease in the relative permeability of aged nanocomposites with increased content of inorganic component as compared with aged pure PI does not correlate with the content of TEOS in contrast to the initial samples of the same composition. PI macrochains chemically bonded to the inorganic phase have limited ability to realize an optimal conformation in the process of thermal relaxation (physical aging) so the increasing the content of the inorganic component has less effect on reducing the permeability of aged composites compared to aged pure PI. This is consistent with changes in the distribution of inorganic aggregates of composites. There are changes in the mean size of aggregates of inorganic particles in the composite and a decrease in their number. Smoothing is observed of the surface of nanocomposite films as well as disappearance of inhomogeneities caused by the surface of support. Due to the chemical bonding of inorganic particles and polyimide matrix, the peculiarities of the physical aging process of such composites are due to the mutual influence of the inorganic and polymer components.

A H2O2-activatable nanoprobe for diagnosing interstitial cystitis and liver ischemia-reperfusion injury via multispectral optoacoustic tomography and NIR-II fluorescent imaging

Developing high-quality NIR-II fluorophores (emission in 1000–1700 nm) for in vivo imaging is of great significance. Benzothiadiazole-core fluorophores are an important class of NIR-II dyes, yet ongoing limitations such as aggregation-caused quenching in aqueous milieu and non-activatable response are still major obstacles for their biological applications. Here, we devise an activatable nanoprobe to address these limitations. A molecular probe named BTPE-NO2 is synthesized by linking a benzothiadiazole core with two tetraphenylene groups serving as hydrophobic molecular rotors, followed by incorporating two nitrophenyloxoacetamide units at both ends of the core as recognition moieties and fluorescence quenchers. An FDA-approved amphiphilic polymer Pluronic F127 is then employed to encapsulate the molecular BTPE-NO2 to render the nanoprobe BTPE-NO2@F127. The pathological levels of H2O2 in the disease sites cleave the nitrophenyloxoacetamide groups and activate the probe, thereby generating strong fluorescent emission (950~1200 nm) and ultrasound signal for multi-mode imaging of inflammatory diseases. The nanoprobe can therefore function as a robust tool for detecting and imaging the disease sites with NIR-II fluorescent and multispectral optoacoustic tomography (MSOT) imaging. Moreover, the three-dimensional MSOT images can be obtained for visualizing and locating the disease foci.