Nanoscopic Level Research Articles

Toward Efficient Utilization of Photogenerated Charge Carriers in Photoelectrochemical Systems: Engineering Strategies from the Atomic Level to Configuration.

Photoelectrochemical (PEC) systems are essential for solar energy conversion, addressing critical energy and environmental issues. However, the low efficiency in utilizing photogenerated charge carriers significantly limits overall energy conversion. Consequently, there is a growing focus on developing strategies to enhance photoelectrode performance. This review systematically explores recent advancements in PEC system modifications, spanning from atomic and nanoscopic levels to configuration engineering. We delve into the relationships between PEC structures, intrinsic properties, kinetics of photogenerated charge carriers, and their utilization. Additionally, we propose future directions and perspectives for developing more efficient PEC systems, offering valuable insights into potential innovations in the field.

Weak signal ultrafast interrogation of a micro-nano FBG probe sensor based on the hybrid amplified dispersion Fourier-transform method.

To elucidate the thermal transport mechanisms at interfaces in micro- and nanoscale electronic devices, real-time monitoring of temperature variations at the microscopic and nanoscopic levels is crucial. Micro-nano fiber Bragg grating (FBG) sensors have been demonstrated as effective in-situ optical temperature probes for measuring local temperatures. Time-stretch dispersion Fourier transform (TS-DFT) that enables fast, continuous, single-shot measurements in optical sensing has been integrated with a micro-nano FBG probe (FBGP) for local temperature sensing. However, its temperature sensitivity and interrogation resolution are limited by the detection sensitivity. In this paper, we propose a hybrid amplified dispersion Fourier transform (ADFT) method to achieve ultrafast interrogation of FBGP's weak signal. Thanks to the combined effect of TS-DFT and hybrid optical amplification, the reflection signal of the FBGP is amplified, and the wavelength shift of the FBGP sensor is converted to a temporal spacing change between two dispersed pulses through dispersion-induced wavelength-to-time mapping. The proposed method uses a homemade dissipative soliton mode-locked laser as the light source. The hybrid optical amplification technique comprises a L-band erbium-doped fiber amplifier and a distributed Raman amplifier. Their noise figure and net gain for the FBGP are 4.81 dB and 15.93 dB, respectively. In addition, the temperature calibration experiments show that a sampling rate of 51.43 MHz and the maximum temperature measurement error of 1.98°C are achieved within the temperature range of 20.3°C to 97°C. The stability of the net gain provided by the hybrid ADFT system is demonstrated by the coefficient of variation, which ranges from 2.22% to 2.95% in the peak voltage signal of the FBGP. This approach applies to scenarios requiring the handling of weak optical signals, particularly in temperature measurement at the micro-nano scale.

Routes to Bidirectional Cathodes for Reversible Aprotic Alkali Metal-CO2 Batteries.

Aprotic alkali metal-CO2 batteries (AAMCBs) have garnered significant interest owing to fixing CO2 and providing large energy storage capacity. The practical implementation of AAMCBs is constrained by the sluggish kinetics of the CO2 reduction reaction (CO2RR) and the CO2 evolution reaction (CO2ER). Because the CO2ER and CO2RR take place on the cathode, which connects the internal catalyst with the external environment. Building a bidirectional cathode with excellent CO2ER and CO2RR kinetics by optimizing the cathode's internal catalyst and environment has attracted most of the attention to improving the electrochemical performance of AAMCBs. However, there remains a lack of comprehensive understanding. This review aims to give a route to bidirectional cathodes for reversible AAMCBs, by systematically discussing engineering strategies of both the internal catalyst (atomic, nanoscopic, and macroscopic levels) and the external environment (photo, photo-thermal, and force field). The CO2ER and CO2RR mechanisms and the "engineering strategies from internal catalyst to the external environment-cathode properties-CO2RR and CO2ER kinetics and mechanisms-batteries performance" relationship are elucidated by combining computational and experimental approaches. This review establishes a fundamental understanding for designing bidirectional cathodes and gives a route for developing reversible AAMCBs and similar metal-gas battery systems.

Characterization of human trabecular bone across multiple length scales using a correlative approach combining X-ray tomography with LaserFIB and plasma FIB-SEM

Three-dimensional correlative multimodal and multiscale imaging is an emerging method for investigating the complex hierarchical structure of biological materials such as bone. This approach synthesizes images acquired across multiple length scales, for the same region of interest, to provide a comprehensive view of the material structure of a sample. Here, we develop a workflow for the structural analysis of human trabecular bone using a femtosecond laser to produce a precise grid to facilitate correlation between imaging modalities and identification of structures of interest, in this case, a single trabecula within a volume of trabecular bone. Through such image registration, high resolution X-ray microscopy imaging revealed fine architectural details, including the cement sheath and bone cell lacunae of the selected bone trabecula. The selected bone volume was exposed with a combination of manual polishing and site-specific femtosecond laser ablation and then examined with plasma focused ion beam-scanning electron microscopy. This reliable and versatile correlation approach has the potential to be applied to a variety of biological tissues and traditional engineered materials. The proposed workflow has the enhanced capability for generating highly resolved and broadly contextualized structural data for a better understanding of the architectural features of a material spanning its macroscopic to nanoscopic levels.

Spatial Visualization of A-to-I Editing in Cells Using Endonuclease V Immunostaining Assay (EndoVIA).

Adenosine-to-inosine (A-to-I) editing is one of the most widespread post-transcriptional RNA modifications and is catalyzed by adenosine deaminases acting on RNA (ADARs). Varying across tissue types, A-to-I editing is essential for numerous biological functions, and dysregulation leads to autoimmune and neurological disorders, as well as cancer. Recent evidence has also revealed a link between RNA localization and A-to-I editing, yet understanding of the mechanisms underlying this relationship and its biological impact remains limited. Current methods rely primarily on in vitro characterization of extracted RNA that ultimately erases subcellular localization and cell-to-cell heterogeneity. To address these challenges, we have repurposed endonuclease V (EndoV), a magnesium-dependent ribonuclease that cleaves inosine bases in edited RNA, to selectively bind and detect A-to-I edited RNA in cells. The work herein introduces an endonuclease V immunostaining assay (EndoVIA), a workflow that provides spatial visualization of edited transcripts, enables rapid quantification of overall inosine abundance, and maps the landscape of A-to-I editing within the transcriptome at the nanoscopic level.

Nanoscopic Characterization of Starch-Based Biofilms Extracted from Ecuadorian Potato (Solanum tuberosum) Varieties.

Synthetic plastic polymers are causing considerable emerging ecological hazards. Starch-based biofilms are a potential alternative. However, depending on the natural source and extraction method, the properties of starch can vary, affecting the physicochemical characteristics of the corresponding casted films generated from it. These differences might entail morphological changes at the nanoscale, which can be explored by inspecting their surfaces. Potato (Solanum tuberosum) is a well-known tuber containing a high amount of starch, but the properties of the biofilms extracted from it are dependent on the specific variety. In this research, four Ecuadorian potato varieties (Leona Blanca, Única, Chola, and Santa Rosa) were analyzed and blended with different glycerol concentrations. The amylose content of each extracted starch was estimated, and biofilms obtained were characterized at both macroscopic and nanoscopic levels. Macroscopic tests were conducted to evaluate their elastic properties, visible optical absorption, water vapor permeability, moisture content, and solubility. It was observed that as the glycerol percentage increased, both moisture content and soluble matter increased, while tensile strength decreased, especially in the case of the Chola variety. These results were correlated to a surface analysis using atomic force microscopy, providing a possible explanation based on the topography and phase contrast observations made at the nanoscale.

Investigation of structure, morphology, and corrosion behavior of carboxylic acids/hydroxyapatite/chitosan coatings on Ti discs for implants

Titanium (Ti) and its alloys are widely used in bone defect repair owing to their advantages, including high strength, corrosion resistance, and biocompatibility. The formation of a stable oxide layer on Ti implants enhances the osseointegration process. Nevertheless, additional progress is required to improve the incorporation of these implants at the microscopic and nanoscopic levels to achieve a biocompatible interface. The main objective of this study was to enhance the morphology of hydroxyapatite and the corrosion resistance of Ti implants by applying hydroxyapatite/chitosan (HA/Cs) nanocomposite coatings embedded with carboxylic acids. The coatings were fabricated by electrodeposition, wherein various acid concentrations (acrylic and acetic acids) were employed as Cs electrolyte solvents to enhance the adhesion and bond strength with the titanium metal substrate. The microstructures of the HA/Cs coatings were analyzed using X-ray diffraction. The results demonstrated that the structure of HA was affected by the type of acid used and its concentration as the crystallinity increased with a high concentration of acrylic acid. Additionally, the morphology of HA/Cs was analyzed using a transmission electron microscope. The results showed that the morphology of HA/Cs changed from a hexagonal rod-like shape with acrylic acid samples into a needle-like shape in acetic acid samples. The corrosion behavior was investigated using electrochemical impedance spectroscopy (EIS) in a simulated body fluid (SBF) at 37±2ºC. The EIS results showed a high corrosion resistance with phase angles close to −80° and high impedance values of 80.5 kΩ cm2 with a high concentration of acrylic acid. These results indicated the formation of a highly adhesive and stable film on the implants in the test solution. In conclusion, based on this study and our previous work, the corrosion resistance, good biocompatibility, and biomineralization properties of the prepared HA/Cs-coated Ti recommend it as an alternative implant for clinical applications.

Molecular Probing of the Microscopic Pressure at Contact Interfaces.

Obtaining insights into friction at the nanoscopic level and being able to translate these into macroscopic friction behavior in real-world systems is of paramount importance in many contexts, ranging from transportation to high-precision technology and seismology. Since friction is controlled by the local pressure at the contact it is important to be able to detect both the real contact area and the nanoscopic local pressure distribution simultaneously. In this paper, we present a method that uses planarizable molecular probes in combination with fluorescence microscopy to achieve this goal. These probes, inherently twisted in their ground states, undergo planarization under the influence of pressure, leading to bathochromic and hyperchromic shifts of their UV-vis absorption band. This allows us to map the local pressure in mechanical contact from fluorescence by exciting the emission in the long-wavelength region of the absorption band. We demonstrate a linear relationship between fluorescence intensity and (simulated) pressure at the submicron scale. This relationship enables us to experimentally depict the pressure distribution in multiasperity contacts. The method presented here offers a new way of bridging friction studies of the nanoscale model systems and practical situations for which surface roughness plays a crucial role.

Nanoparticles as Drug Delivery Carrier-synthesis, Functionalization and Application.

In recent years, advancements in chemistry have allowed the tailoring of materials at the nanoscopic level as needed. There are mainly four main types of nanomaterials used as drug carriers:metal-based nanomaterials, organic nanomaterials, inorganic nanomaterials, and polymer nanomaterials. The nanomaterials as a drug carrier showed advantages for decreased side effects with a higher therapeutic index. The stability of the drug compounds is increased by encapsulation of the drug within the nano-drug carriers, leading to decreased systemic toxicity. Nano-drug carriers are also used for controlled drug release by tailoring system-made solubility characteristics of nanoparticles by surface coating with surfactants. The review focuses on the different types of nanoparticles used as drug carriers, the nanoparticle synthesis process, techniques of nanoparticle surface coating for drug carrier purposes, applications of nano-drug carriers, and prospects of nanomaterials as drug carriers for biomedical applications.

In silico study of therapeutic deep eutectic solvent for tetracaine liquid delivery

The development of a drug delivery liquid formulation of ester – based tetracaine local anaesthetic is synthesised in silico via the formation of a therapeutic deep eutectic solvent in combination with citral, a natural monoterpenoid. The properties of the obtained liquid system, studied at the nanoscopic level, are derived from a combination of quantum chemistry and classical molecular dynamics simulations. The intermolecular forces (hydrogen bonding) were analysed and their relationship with liquid phase properties were established. Water effect on the liquid phase properties were also considered in terms of competing for hydrogen bonding sites in the components of the developed fluid. The systems proposed in this work were studied using CIT (HBA) 1:1 TET (HBD) molar ratio at temperatures ranging from 288 K to 318 K and 1 bar. The hydrogen bond network developed between the oxygen atom in citral molecules and the –NH group in tetracaine molecules under those conditions, confirmed via minimal cluster analysis, is maintained during the addition of water up to 1.3 wt% as the water molecules do not disrupt the intermolecular hydrogen bond but develop new interactions (hydrogen bonds) with citral and tetracaine monomers presented in the fluid. The reported results probed the suitability of the considered system as an alternative drug delivery method as well as the possibility of developing deep eutectic-based formulation of anaesthetics using natural compounds due to the formation of effective and strong intermolecular hydrogen bonds.

High throughput spectrally resolved super-resolution fluorescence microscopy with improved photon usage.

Single-molecule localization microscopy (SMLM), a type of super-resolution fluorescence microscopy, has become a strong technique in the toolbox of chemists, biologists, physicists, and engineers in recent years for its unique ability to resolve characteristic features at the nanoscopic level. It drastically improves the resolution of optical microscopes beyond the diffraction limit, with which previously unresolvable structures can now be studied. Spectrally resolved super-resolution fluorescence microscopy via multiplexing of different fluorophores is one of the greatest advancements among SMLM techniques. However, current spectrally resolved SMLM (SR-SMLM) methodologies present low spatial resolution due to loss of photons, low throughput due to spectral interferences, or require complex optical systems. Here, we overcome these drawbacks by developing a SR-SMLM methodology using a color glass filter. It enables high throughput and improved photon usage for hyperspectral imaging at the nanoscopic level. Our methodology can readily distinguish fluorophores of close spectral emission and achieves sub-10 nm localization and sub-5 nm spectral precisions.

Metal-free functionalization of tyrosine residues in short peptides and study of the morphological alterations.

An efficient functionalization of tyrosine residues in phenolic regions is achieved under metal-free conditions. The strategy involves the conversion of a tyrosine residue to 4-amino phenylalanine or 4-amino-3-methoxy phenylalanine in short peptides through a controlled oxidative dearomatization. This transformation is achieved in one pot with good yields and excellent regioselectivity. Consequently, the self-assembly of the peptide compounds has been studied at the nanoscopic level before and after functionalization. The results suggest that the peptide derivatives comprising amide groups promote intermolecular H-bonding interactions and the difference in -OH and -NH2 functional groups is found to be responsible for the morphological changes. Morphological transitions from 1D nanowires to 2D nanosheets were observed during functional group modification.

Post‐Synthetic Ensembling Design of Hierarchically Ordered FAU‐type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking

AbstractZeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well‐organized hierarchically porous architecture can efficiently overcome their intrinsic mass‐transfer limitations without losing hydrothermal stability. We report a rational post‐synthetic design for synthesizing hierarchically ordered FAU‐type zeolites exhibiting 2D‐hexagonal (P6mm) and 3D‐cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit‐cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant‐zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion‐specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle‐distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Analysis of mortars with old plastering waste using state-of-the-art method: nuclear magnetic resonance

One of the major problems we face today is the correct management of waste generated in all spheres of activity. Thus, the concept of sustainable development aims to develop strategies that prevent and solve problems already generated. Domain construction is the one that generates the most waste worldwide, according to recent studies, which requires the imposition of clear, effective, and future-proof measures to improve the environment and the health of the population. This paper is the continuation of a research program in which 3 types of mortar recipes are analyzed. The study involves replacement of aggregates, in different percentages (10% and 15%), with plaster waste from historic buildings. The obtained results show that the values fall within the limits stipulated in the norms in force, so the study will continue with the analysis of the samples using the state-of-the-art method: nuclear magnetic resonance. The paper aims to analyze the properties of the proposed mortars at the nanoscopic level, following the relationship between the plaster mortar matrix and the plaster waste introduced in different percentages in the samples. In addition, the impact of these wastes on the hydration of the cement and on the porosity of the composition of these mortars is also observed, being noticed that the relationship between the porosity of the samples and the mechanical resistances is inversely proportional, that is, the resistances decrease as the porosity increases. It will also be identified the location of hydrogen in the structure: in hydrated mineralogical compounds of cement and in large, medium and small pores. For each studied sample, the investigations were conducted at the age of 7, 14 and 28 days (even at 3 days for samples with 10% and 15% substitution of aggregates with old plastering mortars). The results for the proposed samples will be compared to the standard recipe.

Tendon collagen fibril morphology and nano-mechanics via atomic force microscopy

Due to the hierarchical structure of tendon tissue (fascicles→fibers→fibrils), it is essential to investigate morphology and mechanics at the nano-scopic level to better understand whole body function. Previous studies investigating changes in tendon mechanics after exercise/disease/unloading have focused on the whole tendon and fascicle levels, but limited data exists on adaptations at the collagen fibril level. Objective: Provide a new method to study previously frozen tendon tissue by investigating collagen fibril 1) morphology, 2) nano-mechanical properties, and 3) elasticity maps using atomic force microscopy (AFM). Hypothesis: This method will provide a reliable way to assess tendon structure and function at the nano-scale. Methods: C57BL/6J mouse tendons from NASA Rodent Research-1 (-80°C) were chemically separated and mounted onto glass slides then mechanically separated into tendon subunit sheets and left to air-dry. Collagen fibril morphology was tested with a JPK Nanowizard 4a in tapping mode with a Tap300Al-G cantilever (tip radius=10nm, k=40N/m). Samples were then rehydrated for mechanical testing in Quantitative Imaging (QI) mode with an SNL-10D cantilever (tip radius=2nm, k=0.06N/m). Force data acquisition took place in liquid with a set point of 2nN and Z-speed of 40μm/s. Force-microscopy (FM) and structural data were processed using JPK Data Processing Software and Gwyddion, respectively. Data: Tendon collagen fibrils exhibited uniform D-periods across 38 fibril sections (D-period: 66nm±2.1, diameter: 63nm±23.5). Quantitative analysis of the force curves (n=30) along the highest point of the fibril revealed an average Young’s Modulus (YM) of 2.53MPa±0.31. Elasticity maps (n=3) highlighting the distribution of mechanical properties were generated using FM data. Results Summary: Our tissue preparation protocol combined with AFM reliably determines collagen fibril morphology and nano-mechanical properties of mouse tendons that were previously frozen. As evidence, we present systematic YM within and across different data sets. In addition, the YM values were found to be consistent with previous measurements in tendon tissue under similar conditions. Elasticity maps produced by analysis of FM data indicate the similarity of YM values across the tendon surface. Tendon fibrils were found to have similar D-periodicity despite the variation in fibril size, which is consistent with previous literature. Conclusions: This research provides a new method to test tendon collagen fibril structure and mechanical properties at the nano-scale, presenting a novel analysis (elasticity maps) showing contrast in YM across the fibril surface. Funding: CSUPERB New Investigator Grant to JRB This is the full abstract presented at the American Physiology Summit 2023 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

Quantitative, Spectro-kinetic Analysis of Oxygen in Electron-Beam Sensitive, Multimetallic Oxide Nanostructures.

The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content of nanostructures of electron-beam sensitive oxides. Kinetic modeling of O-stoichiometry data provided K0.13MnO1.98 as overall composition for nanorods of the hollandite. The quantitative agreement, within a 1% mol error, observed with results obtained by macroscopic techniques (temperature-programmed reduction and neutron diffraction) validate the proposed methodology for the quantitative analysis, at the nanoscale, of light elements, as it is the case of oxygen, in the presence of heavy ones (K, Mn) in the highly compromised case of nanostructured materials which are prone to electron-beam reduction. Moreover, quantitative comparison of oxygen evolution data measured at macroscopic and nanoscopic levels allowed us to rationalize beam damage effects in structural terms and clarify the exact nature of the different steps involved in the reduction of these oxides with hydrogen.

Recent advances in the application of atomic force microscopy to structural biology

The application of atomic force microscopy (AFM) for functional imaging and manipulating biomolecules at all levels of organization has enabled great progress in the structural biology field over the last decades, contributing to the discovery of novel structural entities of biological significance across many disciplines ranging from biochemistry, biomedicine and biophysics to molecular and cell biology, up to food systems and beyond. AFM has the capability to generate high-resolution topographic images spanning from the submolecular to the (sub)cellular range and can probe biochemical and biophysical sample properties in close to native conditions with excellent temporal resolution. Instrumental developments in the past decade enable dynamical structural and conformational studies of single biomolecules and new techniques for structural and chemical modification of the AFM probe have converted the cantilever into a versatile tool to study different biological phenomena, such as the mechanical stability of biomolecular complexes or the force induced dynamic changes of mechanically stressed proteins at the nanoscopic level. To improve the functionality of AFM and approach dynamic processes of complex biological systems ex vivo, AFM is combined with complementary microscopy, nanoscopy and spectroscopy tools. These multimethodological approaches provide unprecedented possibilities of probing physical, chemical and biological properties of complex cellular systems with high spatio-temporal resolution, leading to novel applications that correlate structural results with functional biochemical, biophysical, immunological, or genetic data of the system under study.

Revealing the tissue-level complexity of endogenous glucagon-like peptide-1 receptor expression and signaling

The glucagon-like peptide-1 receptor (GLP1R) is a class B G protein-coupled receptor (GPCR) involved in glucose homeostasis and food intake. GLP1R agonists (GLP1RA) are widely used in the treatment of diabetes and obesity, yet visualizing the endogenous localization, organization and dynamics of a GPCR has so far remained out of reach. In the present study, we generate mice harboring an enzyme self-label genome-edited into the endogenous Glp1r locus. We also rationally design and test various fluorescent dyes, spanning cyan to far-red wavelengths, for labeling performance in tissue. By combining these technologies, we show that endogenous GLP1R can be specifically and sensitively detected in primary tissue using multiple colors. Longitudinal analysis of GLP1R dynamics reveals heterogeneous recruitment of neighboring cell subpopulations into signaling and trafficking, with differences observed between GLP1RA classes and dual agonists. At the nanoscopic level, GLP1Rs are found to possess higher organization, undergoing GLP1RA-dependent membrane diffusion. Together, these results show the utility of enzyme self-labels for visualization and interrogation of endogenous proteins, and provide insight into the biology of a class B GPCR in primary cells and tissue.

Tuning Human Serum Albumin (HSA) Hydrogels through Albumin Glycation.

The changes of technological properties of albumin-based hydrogels induced by increasing degrees of post-translational modification of the protein are reported. Maillard-type modification of amino acids arginine and lysine of albumin is achieved through glyoxal as an α-dicarbonyl compound. The degrees of modification are fine-tuned using different molar ratios of glyoxal. Hydrogels are thermally induced by heating highly concentrated precursor solutions above the protein's denaturation temperature. While the post-translational modifications are determined and quantified with mass spectrometry, continuous-wave (CW) electron paramagnetic resonance(EPR) spectroscopy shed light on the protein fatty acid binding capacity and changes thereof in solution and in the gel state. The viscoelastic behavior is characterized as a measure of the physical strength of the hydrogels. On the nanoscopic level, the modified albumins in low concentration solution reveal lower binding capacities with increasing degrees of modification. On the contrary, in the gel state, the binding capacity remains constant at all degrees of modifications. This indicates that the loss of fatty acid binding capacity for individual albumin molecules is partially compensated by new binding sites in the gel state, potentially formed by modified amino acids. Such, albumin glycation offers a fine-tuning method of technological and nanoscopic properties of these gels.