The Interplay of Conjugation and Metal Coordination in Tuning the Electron Transfer Abilities of NTA-Graphene Based Interfaces

An artificial leaf is a concept that not only replicates the processes taking place during natural photosynthesis but also provides a source of clean, renewable energy. One important part of such a device are molecules that stabilize the connection between the bioactive side and the electrode, as well as tune the electron transfer between them. In particular, nitrilotriacetic acid (NTA) derivatives used to form a self-assembly monolayer chemisorbed on a graphene monolayer can be seen as a prototypical interface that can be tuned to optimize the electron transfer. In the following work, interfaces with modifications of the metal nature, backbone saturation, and surface coverage density are presented by means of theoretical calculations. Effects of the type of the metal and the surface coverage density on the electronic properties are found to be key to tuning the electron transfer, while only a minor influence of backbone saturation is present. For all of the studied interfaces, the charge transfer flow goes from graphene to the SAM. We suggest that, in light of the strength of electron transfer, Co2+ should be considered as the preferred metal center for efficient charge transfer.

Design and Experimental Evaluation of an Aerial Solution for Visual Inspection of Tunnel-like Infrastructures

Current railway tunnel inspections rely on expert operators performing a visual examination of the entire infrastructure and manually annotating encountered defects. Automatizing the inspection and maintenance task of such critical and aging infrastructures has the potential to decrease the associated costs and risks. Contributing to this aim, the present work describes an aerial robotic solution designed to perform autonomous inspections of tunnel-like infrastructures. The proposed robotic system is equipped with visual and thermal sensors and uses an inspection-driven path planning algorithm to generate a path that maximizes the quality of the gathered data in terms of photogrammetry goals while optimizing the surface coverage and the total trajectory length. The performance of the planning algorithm is demonstrated in simulation against state-of-the-art methods and a wall-following inspection trajectory. Results of a real inspection test conducted in a railway tunnel are also presented, validating the whole system operation.

Interfacial properties of chitosan lactate at the liquid/air interface

The interfacial properties (dynamic and equilibrium surface tension, viscosity and elasticity moduli) of chitosan lactate have been studied at the liquid/air interface by the oscillating drop shape method. Isotherms of dynamic surface tension of chitosan lactate are similar to dependences for other polyelectrolyte solutions, in particular for proteins. Chitosan is a weak cationic polyelectrolyte which can change its conformation from a linear rod to a chaotic and compacted coil. Therefore, the experimental dependence of the equilibrium surface tension on concentration of chitosan lactate was analyzed with the adsorption model proposed earlier for proteins. This model accounts the possibility of polyelectrolyte molecules existence in surface layer in n states with different molar surface varying from the maximum value at very low surface coverage by polyelectrolyte molecules to a minimum value at high surface coverage. Good agreement between the calculated and experimental values of surface tension was observed. The dependences of the elasticity and viscosity moduli of chitosan lactate solutions on the drop oscillations frequency are conditioned by the influence of exchange processes both between the surface layer and the bulk solution and in the surface layer itself. An increase of the solution concentration intensifies the exchange processes, and an increase of the oscillation frequency suppresses them. It is shown that the dependence of the surface viscoelasticity modulus of chitosan lactate is extreme in nature with a pronounced maximum. The reason for such behavior is the possibility of changing the molar surface area of the polyelectrolyte at the interface dependent on the amount of adsorption and its structural properties. Attempt of theoretical description of the viscoelasticity modulus within the framework of model accounting mono- or bilayer adsorption did not lead to a satisfactory result, possibly due to barrier adsorption mechanism of chitosan. But bilayer model provide qualitative description of extreme behavior of surface viscoelasticity on concentration. The values of the surface viscoelasticity modulus of chitosan lactate occupy an intermediate position in comparison with the data available in the literature for globular and flexible-chain proteins, that is consistent with their molecular structure. In addition, the work shows the applicability of the adsorption model, developed earlier for proteins in the framework of a nonideal two-dimensional solution theory, for describing the surface properties of other polyelectrolytes. This makes it possible to obtain qualitative and quantitative information about the processes occurring in the systems under study.

Electrocatalytic Properties of Ni(II) Schiff Base Complex Polymer Films

Platinum electrodes were modified with polymers of the (±)-trans-N,N′-bis(salicylidene)-1,2-cyclohexanediaminenickel(II) ([Ni(salcn)]) and (±)-trans-N,N′-bis(3,3′-tert-Bu-salicylidene)-1,2-cyclohexanediaminenickel(II) ([Ni(salcn(Bu))]) complexes to study their electrocatalytic and electroanalytical properties. Poly[Ni(salcn)] and poly[Ni(salcn(Bu))]) modified electrodes catalyze the oxidation of catechol, aspartic acid and NO2−. In the case of poly[Ni(salcn)] modified electrodes, the electrocatalysis process depends on the electroactive surface coverage. The films with low electroactive surface coverage are only a barrier in the path of the reducer to the electrode surface. The films with more electroactive surface coverage ensure both electrocatalysis inside the film and oxidation of the reducer directly on the electrode surface. In the films with the most electroactive surface coverage, electrocatalysis occurs only at the polymer–solution interface. The analysis was based on cyclic voltammetry, EQCM (electrochemical quartz crystal microbalance) and rotating disc electrode method.

Mathematical Modeling of Cyclic Voltammogram Curves of Copper Deposition

The manufacturing of interconnects and the packaging of integrated circuits are achieved with electrodeposition of copper or other metals. In order to increase the rate of deposition, especially for the large features in packaging, forced convection is provided with certain agitation mechanisms. Although this reduces deposition time, it leads to non-uniform mass transport within each feature and between different features. Special organic additives are used in the solution during the process in order to tune the nucleation and growth of metal, as well as to modify the deposition rate and improve the uniformity. A mathematical model to describe the behavior of organic additives in conjugation with fluid flow and features of various geometry and dimensions is very much desired to facilitate chemistry and process development. In order to achieve this, the physiochemical kinetics of additive and their influence on the Cu deposition rate need to be described precisely. This presentation focuses on a method to extract the kinetic parameters describing the combined effect of multiple additives during copper deposition using rotating disk electrode (RDE). The one-dimensional steady state convection-diffusion equation for each of the chemical species including copper is solved by a semi-analytical method for a range of potentials. The boundary conditions of these differential equations are coupled on the surface of the RDE through the surface coverage of the absorbed species. The steady state of surface coverage of the species represents a dynamic equilibrium of three key processes i.e., adsorption, desorption, and consumption (incorporation). When equilibrium is achieved, the net rate of adsorption and desorption becomes equal to the rate of consumption. At each value of potential, the surface coverage of the additives is solved. At first, the solution is obtained with only one species known as suppressor and it was found that in a specific range of voltage and kinetic parameter multiple solutions of the surface coverage exist at same applied potential. This mathematically explains the S-shaped negative differential resistance (NDR) feature in experimental Cyclic Voltammogram (CV) curves. Figure 1 shows three such experimental S-shaped curves for different concentration of suppressors. The NDR region obtained in the theoretical CV curve is sensitive to the kinetic parameters of the additives. It is possible to match the theoretical and the experimental CV curves by optimizing the kinetic parameters. Determination of the kinetic parameters by particle swarm optimization using experimental data for multiple additive concentration will be discussed in detail in this talk.

Enhanced Flotation Recovery of Fine Molybdenite Particles Using a Coal Tar-Based Collector

Low flotation efficiency has always been a problem in the separation of low-grade molybdenum ores because of the finely disseminated nature and crystal anisotropy of molybdenite. In this study, a novel kerosene–coal tar collector (KCTC) was prepared and used to explore the feasibility of improving the recovery of fine molybdenite particles. The results showed that KCTC achieved better attaching performance than that shown by kerosene, and the surface coverage and attaching rate constant were improved significantly, especially for finer particles of −38 + 20 μm. Compared with kerosene, KCTC showed more affinity for molybdenite particles and greater adsorbed amounts of KCTC on molybdenite particles were achieved. Moreover, the composite collector was shown to float single molybdenite particles of different sizes, and it was found that the recovery of molybdenite particles of different sizes, particularly in the case of those at −20 μm, was improved dramatically by KCTC. The flotation results of actual molybdenum ores further confirmed that KCTC was beneficial to flotation recovery and the selectivity of molybdenite. This indicated that KCTC is a potential collector for the effective flotation of low-grade deposits of molybdenum ores, and more studies should be conducted on further use in industrial practice.

Identification and glass biodeterioration of Chaetomium globosum TTHF1-3 isolated from optical instrument at Thai Hoa, Nghe An province

The colonization and growth of harmful fungi on the glass surface have caused irreversible damage to optical quality. Harmful grades observed on the optical instruments depend on the biological characteristics of fungi that vary from species to species. The present study focused on isolation, identification, and evaluation of glass biodeterioration properties such as organic acid and exopolysaccharide production of fungal strain Chaetomium globosum TTHF1-3 isolated from lens of optical instrument collected at Thai Hoa, Nghe An province. Under microscopic observation, the fungal strain TTHF1-3 cells showed brown or dark brown color perithecia and ascospores. Based on ITS sequence analyses, the strain TTHF1-3 was found to share 100% sequence identity with that of C. globosum species deposited on GenBank (NCBI). A in situ biodeterioration test exhibited the hyphal surface coverage of strain TTHF1-3 reaching 29.77±1.15%, which corresponded to harmful grade 2 based on the ISO 9022-11:2015 criteria. When incubated on MT4 medium containing glucose and mineral elements, the pH values of C. globosum TTHF1-3 culture were significantly decreased from 6.5 to 3.12±0.12, which was in contrast to MT1 medium. In addition, fungal strain TTHF1-3 was able to produce 8.2±0.3 g/L exopolysaccharides. The findings in the present study confirmed that C. globosum TTHF1-3 was harmful fungus responsible for glass biodeterioration.