Electrochemical properties of positive electrode in lead-acid battery modified by ammonium-based ionic liquids

The influence of selected types of ammonium ionic liquid (AIL) additives on corrosion and functional parameters of lead-acid battery positive electrode was examined. AILs with a bisulfate anion used in the experiments were classified as protic, aprotic, monomeric, and polymeric, based on the structure of their cation. Working electrodes consisted of a lead-calcium-tin alloy utilized in the industry for manufacturing current collectors of positive electrodes in lead-acid batteries (LABs). This alloy was used in the first part of the study for the evaluation of corrosion intensity and stability of electrolyte with AIL additives. In the second part, the grid made of the examined alloy was covered with positive active mass, the composition of which was modified by selected AIL. The selection of an appropriate substance was made based on parameters such as corrosion potential, corrosion current, polarization resistance, and hydrogen and oxygen evolution potentials. Techniques such as linear sweep voltammetry, corrosimetry, and electrochemical impedance spectroscopy were used. The conducted measurements revealed that polymeric AIL additive had an exceptionally positive influence on the inhibition of the corrosion process in LAB and electrochemical window of the electrolyte. The influence of this compound on the specific capacity and resistance of the active mass was also discussed.

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Attachment of Single-Stranded DNA to Certain SERS-Active Gold and Silver Substrates: Selected Practical Tips

Layers formed from single-stranded DNA on nanostructured plasmonic metals can be applied as “working elements” in surface–enhanced Raman scattering (SERS) sensors used to sensitively and accurately identify specific DNA fragments in various biological samples (for example, in samples of blood). Therefore, the proper formation of the desired DNA layers on SERS substrates is of great practical importance, and many research groups are working to improve the process in forming such structures. In this work, we propose two modifications of a standard method used for depositing DNA with an attached linking thiol moiety on certain SERS-active structures; the modifications yield DNA layers that generate a stronger SERS signal. We propose: (i) freezing the sample when forming DNA layers on the nanoparticles, and (ii) when forming DNA layers on SERS-active macroscopic silver substrates, using ω-substituted alkanethiols with very short alkane chains (such as cysteamine or mercaptopropionic acid) to backfill the empty spaces on the metal surface unoccupied by DNA. When 6-mercapto-1-hexanol is used to fill the unoccupied places on a silver surface (as in experiments on standard gold substrates), a quick detachment of chemisorbed DNA from the silver surface is observed. Whereas, using ω-substituted alkanethiols with a shorter alkane chain makes it possible to easily form mixed DNA/backfilling thiol monolayers. Probably, the significantly lower desorption rate of the thiolated DNA induced by alkanethiols with shorter chains is due to the lower stabilization energy in monolayers formed from such compounds.     

Multi-Step Nucleation of a Crystalline Silicate Framework via a Structurally Precise Prenucleation Cluster

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre-organized multi-ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q³₈ polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q³₈ are stabilized by hydrogen bonds with surrounding H₂O and tetramethylammonium ions (TMA⁺). When Q³₈ levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)_x(Q³₈)⋅n H₂O]^(x−8) clathrate complexes into step edges on the crystals.     

Mechanisms of Biomolecular Self-Assembly Investigated Through In Situ Observations of Structures and Dynamics

Biomolecular self-assembly of hierarchical materials is a precise and adaptable bottom-up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning-based approaches, multiparametric characterization, and high-throughput methods can boost the development of biomolecular self-assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self-assembly and to inspire the next generation of biomimetic materials.