Search for: All records

Raman microscopy is a powerful analytical technique for materials and life sciences that enables mapping the spatial distribution of the chemical composition of a sample. State-of-the-art Raman microscopes, based on point-scanning frequency-domain detection, have long (∼1s) pixel dwell times, making it challenging to acquire images of a significant area (e.g., 100×100µm). Here we present a compact wide-field Raman microscope based on a time-domain Fourier-transform approach, which enables parallel acquisition of the Raman spectra on all pixels of a 2D detector. A common-path birefringent interferometer with exceptional delay stability and reproducibility can rapidly acquire Raman maps (∼30min for a 250000pixel image) with high spatial (<1µm) and spectral (∼23cm⁻¹) resolutions. Time-domain detection allows us to disentangle fluorescence and Raman signals, which can both be measured separately. We validate the system by Raman imaging plastic microbeads and demonstrate its multimodal operation by capturing fluorescence and Raman maps of a multilayer-WSe₂sample, providing complementary information on the strain and number of layers of the material.

 

Enzyme encapsulation in metal-organic frameworks (MOFs)/covalent-organic frameworks (COFs) provides advancement in biocatalysis, yet the structural basis underlying the catalytic performance is challenging to probe. Here, we present an effective protocol to determine the orientation and dynamics of enzymes in MOFs/COFs using site-directed spin labeling and electron paramagnetic resonance spectroscopy. The protocol is demonstrated using lysozyme and can be generalized to other enzymes. 

The optical spectra of transition metal dichalcogenide monolayers are dominated by excitons and trions. Here, we establish the dependence of these optical transitions on the disorder from hyperspectral imaging of h-BN encapsulated monolayer MoSe₂. While both exciton and trion energies vary spatially, these two quantities are almost perfectly correlated, with spatial variation in the trion binding energy of only ∼0.18 meV. In contrast, variation in the energy splitting between the two lowest energy exciton states is one order of magnitude larger at ∼1.7 meV. Statistical analysis and theoretical modeling reveal that disorder results from dielectric and bandgap fluctuations, not electrostatic fluctuations. Our results shed light on disorder in high quality TMDC monolayers, its impact on optical transitions, and the many-body nature of excitons and trions.

 

Stress-strain responses and twinning characteristics are studied for a rolled AZ31B magnesium alloy under three different stress states: tension along the normal direction (NDT), compression along the rolled direction (RDC), and torsion about the normal direction (NDTOR) using companion specimens interrupted at incremental strain levels. Tension twinning is extensively induced in twinning-favorable NDT and RDC. All the six variants of tension twin are activated under NDT, whereas a maximum of four variants is activated under RDC. Under NDTOR, both tension twins and compression twins are activated at relatively large strains and twinning occurs in a small fraction of favored grains rather than in the majority of grains. Secondary and tertiary twins are observed in the favorably-orientated grains at high strain levels. Deformation under each stress state shows three stages of strain hardening rate: fast decrease (Stage I), sequential increase (Stage II), and progressive decrease (Stage III). The increase in the hardening rate, which is more significant under NDT and RDC as compared to NDTOR, is attributed to the hardening effect of twin boundaries and twinning texture-induced slip activities. The hardening effect of twin boundaries include the dynamic Hall-Petch hardening induced by the multiplication of twin boundaries (TBs) and twin-twin boundaries (TTBs) as well as the hardening effect associated with the energetically unfavorable TTB formation. When the applied plastic strain is larger than 0.05 under NDT and RDC, the tension twin volume fraction is higher than 50%. The twinning-induced texture leads to the activation of non-basal slips mainly in the twinned volume, i.e. prismatic slips under NDT and pyramidal slips under RDC. The low work hardening under NDTOR is due to the prevailing basal slips with reduced twinning activities under NDTOR. 

Site-directed spin labeling (SDSL) in combination with electron paramagnetic resonance (EPR) spectroscopy probes the otherwise inaccessible structural information in complex biological systems. We recently extended SDSL-EPR to reveal the relative orientation and backbone dynamics of enzymes upon encapsulation in mesoporous nanostructures, which set the structural basis underlying the observed biocatalytic activity. Our strategy had generated interest in the biocatalysis community, and thus in this resource article, we contribute an introduction to the principles and experimental procedure that generalize SDSL-EPR to heterogeneous biocatalysis. We will focus on enzymes in mesoporous materials with examples demonstrating the methods and cautions of potential pitfalls. The ultimate goal is to provide the biocatalysis community with a powerful resource to fill in a long-standing knowledge gap in heterogeneous biocatalysis and the structure-function relationship of enzymes at the interface of enzyme-mesoporous materials and utilize the structural insights to guide the rational design of porous platforms for enzyme immobilization.