Functional Systems Derived from Nucleobase Self-assembly

Dynamic and reversible non-covalent interactions endow synthetic systems and materials with smart adaptive functions that allow them to response to diverse stimuli, interact with external agents, or repair structural defects. Inspired by the outstanding performance and selectivity of DNA in living systems, scientists are increasingly employing Watson−Crick nucleobase pairing to control the structure and properties of self-assembled materials. Two sets of complementary purine-pyrimidine pairs (guanine:cytosine and adenine:thymine(uracil)) are available that provide selective and directional H-bonding interactions, present multiple metal-coordination sites, and exhibit rich redox chemistry. In this review, we highlight several recent examples that profit from these features and employ nucleobase interactions in functional systems and materials, covering the fields of energy/electron transfer, charge transport, adaptive nanoparticles, porous materials, macromolecule self-assembly, or polymeric materials with adhesive or self-healing ability.     

Elucidating Noncovalent Reaction Mechanisms: G‐Quartet as an Intermediate in G‐Quadruplex Assembly

In analogy to covalent reactions, the understanding of noncovalent association pathways is fundamental to influence and control any supramolecular process. Following an approach that is reminiscent of covalent methodologies, we study here, for the first time, the mechanism of G‐quadruplex formation in organic solvents. Our results support a reaction pathway in which the cation shifts the equilibrium towards a G‐quartet transient intermediate, which then acts as a template in the formation of the G‐quadruplex product.     

Structural and thermal properties of spray-dried methotrexate-loaded biodegradable microparticles

Drug–polymer interactions, structural properties, thermal behavior, and stability of biodegradable microparticles are fundamental aspects in the developing of new polymeric drug delivery systems. In this study, poly (d,l-lactide-co-glycolide) (PLGA) microparticles containing methotrexate (MTX) were successfully obtained by spray drying. Scanning electronic microscopy, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), and drug-loading efficiency were used to investigate the effect of drug–polymer ratio and its interactions, in a new MTX-loaded PLGA spray-dried microparticles. High levels of encapsulation efficiency (about 90 %) and a prevalent spherical shape were identified for different drug–polymer ratios used (9, 18, and 27 % m/m). The thermal analyses (DSC and TG) and XRD indicate that MTX is homogeneously distributed in the polymeric matrix, with a prevalent amorphous state in a stable molecular dispersion. Therefore, a correlation between drug content and the structural-thermal properties of drug-loaded PLGA microparticles was established using the thermal analysis data. The biodegradable microparticle leads to an increment of thermal stability of MTX, confirming that spray drying is an efficient process for obtaining MTX-loaded PLGA microparticles.     

Remote sensing of atmospheric gases with optical correlation spectroscopy and lidar: first experimental results on water vapor profile measurements

In this paper, the first experimental demonstration of the optical correlation spectroscopy lidar (OCS-lidar) is proposed. It is a new active remote sensing methodology to measure range-resolved atmospheric gas concentrations, based on broadband laser spectroscopy and light amplitude modulation. As a first step, a numerical study is performed for OCS-lidar measurements to optimize the accuracy of the range-resolved gas concentration measurement. Then, we demonstrate the ability of the OCS-lidar methodology to monitor the water vapor in the planetary boundary layer using the 4ν 720-nm absorption band. In addition to this first experimental proof, two different experimental configurations are proposed. The amplitude modulation, related to the optical correlation spectroscopy, is operated either at the emission with an active amplitude modulator before the backscattering process, or with passive optical filters on the laser backscattered light. For both configurations, range-resolved gas concentration measurements, achieved with a micro-pulse ground-based OCS-lidar, are presented. An extended discussion presents the mixing-ratio accuracy, which reaches ±1,000 ppm at a 2,000-m range for a range resolution of 200 m. The differences between the two experimental configurations are also discussed.     

Surface tension-driven flow in wickless heat pipes with self-rewetting fluids

Surface tension-driven effects in wickless heat pipes with aqueous solutions of long-chain alcohols are investigated. Flow visualizations and numerical simulation of bubbles behaviour and boiling pattern in transparent capillaries show the potential advantages of “self-rewetting” fluids, i.e. liquid solutions with a non-linear dependence of the surface tension with temperature. Surface tension measurements at different temperatures have been carried out also for a number of ternary aqueous solutions with relatively low freezing points. Some of them interestingly exhibit the same anomalous positive surface tension gradient with temperature as binary self-rewetting solutions. These results may open new horizons toward the development of more efficient heat transfer devices for different applications.     

Determination of arsenic in homeopathic drugs by bromide volatilization-inductively coupled plasma-atomic emission spectrometry

Arsenic in homeopathic drugs was determined by coupling a volatile generation with inductively coupled plasma-atomic emission spectrometry. The method is based on the chemical vaporization of arsenic(III) with bromide ions in sulfuric acid media using a batch procedure and subsequent introduction of the gaseous analyte into the plasma torch. The main and interactive effects of the experimental variables affecting this method were evaluated by a 2-level full factorial design. In optimized conditions by Simplex, the method shows an absolute detection limit (3 s) of 0.28 microg for the injection of 230 microL sample. The precision (% relative standard deviation) of the determination was 4.2% at a level of 50 microg/mL As(III) (n = 5). The interference effect of various ions on the arsenic signal was evaluated.     

A Bayesian Analysis of Plant DNA Length Distribution via κ-Statistics

We report an analysis of the distribution of lengths of plant DNA (exons). Three species of Cucurbitaceae were investigated. In our study, we used two distinct κ distribution functions, namely, κ-Maxwellian and double-κ, to fit the length distributions. To determine which distribution has the best fitting, we made a Bayesian analysis of the models. Furthermore, we filtered the data, removing outliers, through a box plot analysis. Our findings show that the sum of κ-exponentials is the most appropriate to adjust the distribution curves and that the values of the κ parameter do not undergo considerable changes after filtering. Furthermore, for the analyzed species, there is a tendency for the κ parameter to lay within the interval (0.27;0.43).     

Synthesis of 198Au nanoparticles sub 10 nm due optimization on local dose by Monte Carlo simulations for cancer treatment

Journal of Radioanalytical and Nuclear Chemistry - To enhance the biological effects of radiation damage in cancerous cells, we present an alternative approach to the use of gold nanoparticles...     

Elucidating Noncovalent Reaction Mechanisms: G-Quartet as an Intermediate in G-Quadruplex Assembly

In analogy to covalent reactions, the understanding of noncovalent association pathways is fundamental to influence and control any supramolecular process. Following an approach that is reminiscent of covalent methodologies, we study here, for the first time, the mechanism of G-quadruplex formation in organic solvents. Our results support a reaction pathway in which the cation shifts the equilibrium towards a G-quartet transient intermediate, which then acts as a template in the formation of the G-quadruplex product.