Directly visualizing carrier transport and recombination at individual defects within 2D semiconductors

Two-dimensional semiconductors (2DSCs) are promising materials for a wide range of optoelectronic applications. While the fabrication of 2DSCs with thicknesses down to the monolayer limit has been demonstrated through a variety of routes, a robust understanding of carrier transport within these materials is needed to guide the rational design of improved practical devices. In particular, the influence of different types of structural defects on transport is critical, but difficult to interrogate experimentally. Here, a new approach to visualizing carrier transport within 2DSCs, Carrier Generation-Tip Collection Scanning Electrochemical Cell Microscopy (CG-TC SECCM), is described which is capable of providing information at the single-defect level. In this approach, carriers are locally generated within a material using a focused light source and detected as they drive photoelectrochemical reactions at a spatially-offset electrolyte interface created through contact with a pipet-based probe, allowing carrier transport across well-defined, µm-scale paths within a material to be directly interrogated. The efficacy of this approach is demonstrated through studies of minority carrier transport within mechanically-exfoliated n-type WSe₂ nanosheets. CG-TC SECCM imaging experiments carried out within pristine basal planes revealed highly anisotropic hole transport, with in-plane and out-of-plane hole diffusion lengths of 2.8 µm and 5.8 nm, respectively. Experiments were also carried out to probe recombination across individual step edge defects within n-WSe₂ which suggest a significant surface charge (∼5 mC m⁻²) exists at these defects, significantly influencing carrier transport. Together, these studies demonstrate a powerful new approach to visualizing carrier transport and recombination within 2DSCs, down to the single-defect level.

Probe-based electrochemical techniques can be used to map carrier transport and recombination within two-dimensional semiconductors.     

Diverse Reactivity of Dienes with Pentaphenylborole and 1-Phenyl-2,3,4,5-Tetramethylborole Dimer

The reactions of a monomeric borole and a dimeric borole with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were investigated. The monomeric borole reacted at ambient temperature whereas heat was required to crack the dimer to form the monomer and induce reactivity. 2,3-Dimethyl-1,3-butadiene reacts to give diverse products resulting from a cycloaddition process with the B−C moiety of the boroles acting as a dienophile, followed by rearrangements to furnish bicyclic species. For 1,3-cyclohexadiene, a [4+2] process is observed in which 1,3-cyclohexadiene serves as the dienophile and the boroles as the diene partner. The experimental results are corroborated with mechanistic theoretical calculations that indicate boroles can serve as either a diene or dienophile in cycloaddition reactions with dienes.     

Strategies Towards Capturing Nitrogenase Substrates and Intermediates via Controlled Alteration of Electron Fluxes

Nitrogenase utilizes an ATP-dependent reductase to deliver electrons to its catalytic component to enable two important reactions: the reduction of N₂ to NH₄⁺, and the reduction of CO to hydrocarbons. The two nitrogenase-based reactions parallel the industrial Haber–Bosch and Fischer–Tropsch processes, yet they occur under ambient conditions. As such, understanding the enzymatic mechanism of nitrogenase is crucial for the future development of biomimetic strategies for energy-efficient production of valuable chemical commodities. Mechanistic investigations of nitrogenase has long been hampered by the difficulty to trap substrates and intermediates relevant to the nitrogenase reactions. Recently, we have successfully captured CO on the Azotobacter vinelandii V-nitrogenase via two approaches that alter the electron fluxes in a controlled manner: one approach utilizes an artificial electron donor to trap CO on the catalytic component of V-nitrogenase in the resting state; whereas the other employs a mismatched reductase component to reduce the electron flux through the system and consequently accumulate CO on the catalytic component of V-nitrogenase. Here we summarize the major outcome of these recent studies, which not only clarified the catalytic relevance of the one-CO (lo-CO) and multi-CO (hi-CO) bound states of nitrogenase, but also pointed to a potential competition between N₂ and CO for binding to the same pair of reactive Fe sites across the sulfur belt of the cofactor. Together, these results highlight the utility of these strategies in poising the cofactor at a well-defined state for substrate- or intermediate-trapping via controlled alteration of electron fluxes, which could prove beneficial for further elucidation of the mechanistic details of nitrogenase-catalyzed reactions.     

Morphological investigation of polylactide/microfibrillated cellulose composites

Optical microscopy and transmission electron microscopy have been used to investigate the morphology of polylactide (PLA)/microfibrillated cellulose (MFC) composites prepared by: compression molding of wet-comingled MFC and PLA latex or powder, twin-screw extrusion of the wet-comingled compounds, and solvent mixing of PLA with MFC or acetylated MFC. Compression molding of wet-comingled MFC and PLA latex or powder compounds resulted in a cellular MFC network, whereas solvent-cast films showed a more uniform dispersion of MFC fibers. Somewhat lower aggregate diameters observed in the acetylated MFC were assumed to be due to decreased MFC hydrophilicity and improved chemical affinity with the PLA matrix. The MFC networks in the commingled compounds were severely disrupted after twin-screw extrusion. This confirmed the limited deformability of the networks inferred from the extensive syneresis during the initial compression molding step, and accounted for substantial losses in stiffness reinforcement by the MFC after extrusion.     

Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand

The steric effects of substituents on five-membered rings are less pronounced than those on six-membered rings because of the difference in bond angles. Thus, the regioselectivities of reactions of five-membered heteroarenes that occur with selectivities dictated by steric effects, such as the borylation of C−H bonds, have been poor in many cases. We report that the silylation of five-membered-ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of [Ir(cod)(OMe)]₂ (cod=1,5-cyclooctadiene) and a phenanthroline ligand or a new pyridyl-imidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C−H bonds of these rings under conditions that the borylation of C−H bonds with previously reported catalysts formed mixtures of products or products that are unstable. The heteroarylsilane products undergo cross-coupling reactions and substitution reactions with ipso selectivity to generate heteroarenes that bear halogen, aryl, and perfluoroalkyl substituents.     

Purification,Characterization, and Structural Studies of a Sulfatase from Pedobacter yulinensis

Sulfatases are ubiquitous enzymes that hydrolyze sulfate from sulfated organic substrates such as carbohydrates, steroids, and flavones. These enzymes can be exploited in the field of biotechnology to analyze sulfated metabolites in humans, such as steroids and drugs of abuse. Because genomic data far outstrip biochemical characterization, the analysis of sulfatases from published sequences can lead to the discovery of new and unique activities advantageous for biotechnological applications. We expressed and characterized a putative sulfatase (PyuS) from the bacterium Pedobacter yulinensis. PyuS contains the (C/S)XPXR sulfatase motif, where the Cys or Ser is post-translationally converted into a formylglycine residue (FGly). His-tagged PyuS was co-expressed in Escherichia coli with a formylglycine-generating enzyme (FGE) from Mycobacterium tuberculosis and purified. We obtained several crystal structures of PyuS, and the FGly modification was detected at the active site. The enzyme has sulfatase activity on aromatic sulfated substrates as well as phosphatase activity on some aromatic phosphates; however, PyuS did not have detectable activity on 17α-estradiol sulfate, cortisol 21-sulfate, or boldenone sulfate.     

Magnetic alignment in nominally non-magnetic hexagonal metal hydrides: NMR

Powders of three hexagonal metal-hydrides or -deuterides are found to align in 4.4–8.3 T magnetic fields used for NMR. The field-alignment is unexpected, since all three systems have very small susceptibilities, as demonstrated by sharp NMR lines. The extent of alignment runs from nearly complete to barely detectable in ZrBe₂(H,D)_x, LuD₃, and YD₃, respectively. The preferred alignment direction in ZrBe₂(H,D)_x is with the crystallites’ c-axis perpendicular to B, while the c-axis and B tend to be parallel in LuD₃ and YD₃. The susceptibilities χ_|| and χ are determined from bulk magnetization measurements in aligned ZrBe₂H_1.4 powder. The alignment must be considered for proper analysis of NMR spectra in these and related materials.