Herein, we report a conjugation strategy, where we utilize a poly(ethylene oxide) cylindrical molecular brush architecture to design a self-assembled structure for thermal stabilization of enzymes. We demonstrate that the proposed architecture of the moderately stiff polymer ligand results in a significant improvement of biocatalytic activity and thermal stability of lysozyme and trypsin that retain their activity, even upon heating to 100 °C and above. The molecular brush is bound via epoxy functional groups to the amino groups of the lysine on the surface of the enzyme globule, promoting the formation of stiff and crowded cages around the enzymes and preventing the water molecules access to the enzyme and enzymes agglomeration. The molecular dynamic simulations show that the high concentration of poly(ethylene oxide) in the vicinity of the enzyme is critical for their stability. Monitoring of lysozyme–molecular brush conjugates for 6 and 12 months in lyophilized form and in solution, respectively, has shown that the conjugation does not compromise the shelf life of the enzyme.
The rapid development of spectral-imaging methods in scanning probe, electron, and optical microscopy in the last decade have given rise for large multidimensional datasets. In many cases, the reduction of hyperspectral data to the lower-dimension materialsspecific parameters is based on functional fitting, where an approximate form of the fitting function is known, but the parameters of the function need to be determined. However, functional fits of noisy data realized via iterative methods, such as least-square gradient descent, often yield spurious results and are very sensitive to initial guesses. Here, we demonstrate an approach for the reduction of the hyperspectral data using a deep neural network approach. A combined deep neural network/least-square approach is shown to improve the effective signal-to-noise ratio of band-excitation piezoresponse force microscopy by more than an order of magnitude, allowing characterization when very small driving signals are used or when a material's response is weak.
Unique optoelectronic, electronic, and sensing properties of hybrid organic–inorganic perovskites (HOIPs) are underpinned by the complex interactions between electronic and ionic states. Here, the photoinduced field ion migration in HOIPs is directly observed. Using newly developed local probe time‐resolved techniques, more significant CH3NH3+ migration than I−/Br− migration in HOIPs is unveiled. It is found that light illumination only induces CH3NH3+ migration but not I−/Br− migration. By directly observing temporal changes in bias‐induced and photoinduced ion migration in device conditions, it is revealed that light illumination suppresses the bias‐induced ion redistribution in the lateral device. These findings, being a necessary compensation of previous understandings of ion migration in HOIPs based on simulations and static and/or indirect measurements, offer advanced insights into the distinct light effects on the migration of organic cation and halides in HOIPs, which are expected to be helpful for improving the performance and the long‐term stability of HOIPs optoelectronics.
Multimodal chemical imaging simultaneously offers high-resolution chemical and physical information with nanoscale and, in select cases, atomic resolution. By coupling modalities that collect physical and chemical information, we can address scientific problems in biological systems, battery and fuel cell research, catalysis, pharmaceuticals, photovoltaics, medicine, and many others. The combined systems enable the local correlation of material properties with chemical makeup, making fundamental questions of how chemistry and structure drive functionality approachable. In this Review, we present recent progress and offer a perspective for chemical imaging used to characterize a variety of samples by a number of platforms. Specifically, we present cases of infrared and Raman spectroscopies combined with scanning probe microscopy; optical microscopy and mass spectrometry; nonlinear optical microscopy; and, finally, ion, electron, and probe microscopies with mass spectrometry. We also discuss the challenges associated with the use of data originated by the combinatorial hardware, analysis, and machine learning as well as processing tools necessary for the interpretation of multidimensional data acquired from multimodal studies.
Given the remarkable performance of hybrid organic–inorganic perovskites (HOIPs) in solar cells, light emitters, and photodetectors, the quest to advance the fundamental understanding of the photophysical properties in this class of materials remains highly relevant. Recently, the discovery of ferroic twin domains in HOIPs has renewed the debate of the ferroic effects on optoelectric processes. This work explores the interaction between light and ferroic twin domains in CH3NH3PbI3. Due to strain and chemical inhomogeneities, photogenerated electrons and holes show a preferential motion in the ferroelastic twin domains. Density functional theory (DFT) shows that electrons and holes result in lattice expansion in CH3NH3PbI3 differently. Hence, light generates strain in the ferroelastic domains due to preferential photocarrier motion, leading to a screening of strain variation. X‐ray diffraction studies verify the DFT simulations and reveal that the photoinduced strain is light intensity dependent, and the photoexcitation is a prerequisite of inducing strain by light. This work extends the fundamental understanding of light‐ferroic interaction and offers guidance for developing functional devices.
The contrast formation mechanism in nanoscale Infrared (IR) Spectroscopy is analyzed. The temperature distribution and elastic displacement across the illuminated T-shape boundary between two materials with different IR-radiation absorption coefficients and thermo-physical and elastic properties located on a rigid substrate are calculated self-consistently for different frequencies f ∼ (1 kHz–1 MHz) of IR-radiation modulation (fully coupled problem). Analytical expressions for the temperature and displacement profiles across the “thermo-elastic step” are derived in the decoupling approximation for f = 0 (“static limit”), and conditions for approximation validity at low frequencies of IR-modulation are established. The step height was found to be thickness-independent for thick layers and proportional to the square of the thickness for very thin films. The theoretical results will be of potential interest for applications in the scanning thermo-ionic and thermal infrared microscopies for relatively long sample thermalization times and possibly for photothermal induced resonance microscopy using optomechanical probes.
Precursors derived from the hydrolysis of organic or inorganic salts have been widely used to produce ceramic coatings for a broad variety of applications. When applying the liquid precursors to the substrates, it is extremely challenging to control the film uniformity and homogeneity. The rate of solvent evaporation at different locations is different, causing the viscosity variation and flows in the film. There is very limited knowledge about the viscosity change in evaporating ceramic precursors. Therefore, it is crucial to understand the effect of evaporation on viscosity variation in thin films and droplets. We use magnetic rotational spectroscopy to study the time dependence of viscosity in mullite precursors. A correlation between the viscosity change and evaporation kinetics is revealed. This correlation was used to relate the change of viscosity to the concentration of mullite. A master curve relating viscosity to the mullite concentration was constructed and used to propose a possible scenario of the viscosity increase during solvent evaporation.
The gap in understanding how underlying chemical dynamics impact the functionality of metal halide perovskites (MHPs) leads to the controversy about the origin of many phenomena associated with ion migration in MHPs. In particular, the debate regarding the impact of ion migration on current-voltage (I-V) hysteresis of MHPs devices has lasted for many years, where the difficulty lies in directly uncovering the chemical dynamics, as well as identifying and separating the impact of specific ions. In this work, using a newly developed time-resolved time-of-flight secondary ion mass spectrometry CH 3 NH 3 + and I − migrations in CH 3 NH 3 PbI 3 are directly observed, revealing hysteretic CH 3 NH 3 + and I − migrations. Additionally, hysteretic CH 3 NH 3 + migration is illumination-dependent. Correlating these results with the I-V characterization, this work uncovers that CH 3 NH 3 + redistribution can induce a remanent field leading to a spontaneous current in the device. It unveils that the CH 3 NH 3 + migration is responsible for the illumination-associated I-V hysteresis in MHPs. Hysteretic ion migration has not been uncovered and the contribution of any ions (e.g., CH 3 NH 3 +) has not been specified before. Such insightful and detailed information has up to now been missing, which is critical to improving MHPs photovoltaic performance and developing MHPs-based memristors and synaptic devices. Metal halide perovskites (MHPs), as a class of outstanding optoelectronic materials, [1] have attracted tremendous research interests in the past decade. [2] MHPs show lots of interesting
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