While both films exhibit homogeneous O and V content, they are also characterized by local regions of Cu enrichment and depletion that extend beyond individual grains. By contrast, Cu-rich photoelectrodes exhibit a tendency toward CuO secondary phase formation and a significantly reduced photoelectrochemical activity, indicating a significantly poor electronic tolerance to Cu-enrichment. These findings highlight that the average film composition at the macroscale is insufficient for defining structure-function relationships in complex ternary compounds. Rather, correlating microscopic variations in chemical composition to macroscopic photoelectrochemical performance provides insights into photocatalytic activity and stability that are otherwise not apparent from pure macroscopic characterization.ConspectusAlthough electrochemical energy storage is commonplace in our society, further advancements in this technology are indispensable for the transition to a low-carbon society. Recent intensive research has expanded concepts in this field; however, finding one suitable material to obtain a high energy density accomplishing the criteria of next-generation batteries is still a conundrum. To solve this issue, material investigations based on big data combined with artificial intelligence are a present trend. On the contrary, this Account focuses on an alternative approach, i.e., fundamental research to shed light on key basic principles to design new electrode materials and new principles achieving multielectron transfer, which is a key to improve a specific capacity. In addition to the cation-redox mechanism, materials showing the multielectron-transfer mechanism based on cation-/anion-redox can enrich material choices with high theoretical energy densities. The challenge in this mechanism is that a ratioovide unique electronic states. These electronic states are projections of intriguing electrochemical features in this materials system, such as cation/anion co-redox mechanism, anion-insertion mechanism, or inductive effect. This Account indicates that 2D π-conjugated frameworks can be applied as models to extract fundamental/microscopic principles in the complicated electrode processes, which is linked to practical electrode materials, such as oxides. Therefore, the approach shown here is a powerful tool to unveil microscopic electrochemical energy storage mechanisms, which is indispensable to advance clean energy technology and accelerate decarbonization.Molecular spur gear dynamics with high gearing fidelity can be achieved through a careful selection of constituent molecular components that favorably position and maintain the two gears in a meshed configuration. Here, we report the synthesis of a new macrocyclic molecular spur gear with a bibenzimidazole stator combined with a second naphthyl bis-gold-phosphine gold complex stator to place two 3-fold symmetric 9,10-diethynyl triptycene cogs at the optimal distance of 8.1 Å for gearing. Micro electron diffraction (μED) analysis confirmed the formation of the macrocyclic structure and the proper alignment of the triptycene cogs. Gearing dynamics in solution are predicted to be extremely fast and, in fact, were too fast to be observed with variable-temperature 1H NMR using CD2Cl2 as the solvent. A combination of molecular dynamics and metadynamics simulations predict that the barriers for gearing and slippage are ca. 4 kcal mol-1 and ca. https://www.selleckchem.com/products/ak-7.html 9 kcal mol-1, respectively. This system is characterized by enhanced gearing fidelity compared to the acyclic analog. This is achieved by rigidification of the structure, locking the two triptycenes in the preferred gearing distance and orientation.A sustainable three-electrode platform for affordable microfluidic electroanalysis is described. The device can be handmade using common tools and, facilitating broad applicability, is indefinitely reusable through simple surface polishing. Compact prototypes with Pt counter, Pt working, and Ag/AgCl reference electrode disks were combined with silicone lid plates containing a microchannel for electrolyte flow. Redox voltammetry/amperometry of excellent quality was achieved in static and flowing ferricyanide solutions, respectively. Modified with a glucose oxidase surface layer, base plate Pt WEs performed very well as amperometric biosensors for microfluidic blood glucose testing. The electrode system is recyclable, compatible with matching lid plate microchannels, and functionally adaptable regarding the constituent metal and electrode surface modifications. This asset combination makes the device a sustainable detection tool for microfluidic electroanalysis, with applications ranging from direct detection of redox-active analytes to bioreceptor-assisted biosensing. It avoids costly microfabrication with clean-room use, and the accessibility of microfluidic EC (bio)sensing is thus greatly increased, especially for users with restricted budgets.An azide-functionalized 12-armed Buckminster fullerene has been monosubstituted in organic media with a substoichiometric amount of cyclooctyne-modified oligonucleotides. Exposing the intermediate products then to the same reaction (i.e., strain-promoted alkyne-azide cycloaddition, SPAAC) with an excess of slightly different oligonucleotide constituents in an aqueous medium yields molecularly defined monofunctionalized spherical nucleic acids (SNAs). This procedure offers a controlled synthesis scheme in which one oligonucleotide arm can be functionalized with labels or other conjugate groups (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, DOTA, and Alexa-488 demonstrated), whereas the rest of the 11 arms can be left unmodified or modified by other conjugate groups in order to decorate the SNAs' outer sphere. Extra attention has been paid to the homogeneity and authenticity of the C60-azide scaffold used for the assembly of full-armed SNAs.The structure of the novel Zintl phase, Cs5NbAs10, is reported for the first time. This compound crystallizes in the monoclinic P21/c space group (no. 14) with eight formula units per cell. The structure represents a unique atomic arrangement, constituting a new structure type with Wyckoff sequence e32. The most important structural element is the unprecedented [Nb(As5)2]5- cluster anion, formed by a Nb atom enclosed between two As5 rings. These nonaromatic cyclic species, formally [As5]5-, adopt an envelope conformation similar to that of cyclopentane. To date, it is only the second example of an [As5]5- ring with this conformation, reported in an inorganic solid-state compound. The bonding characteristics of the [Nb(As5)2]5- cluster and the [As5]5- rings are thoroughly investigated using first-principles methods and discussed. Electronic band structure calculations on Cs5NbAs10 suggest that this compound is a semiconductor with an estimated band gap of ca. 1.4 eV.