Quantitative Interpretation of Potentiodynamic Polarization Curves Obtained at High Scan Rates in Scanning Electrochemical Cell Microscopy.

Scanning electrochemical cell microscopy is becoming the tool of choice for the investigation of localized metal corrosion. Typically, potentiodynamic polarization measurements in scanning electrochemical cell microscopy are performed at high potential scan rates. However, Tafel extrapolation applied to high-scan-rate potentiodynamic polarization curves would yield inaccurate corrosion kinetics due to the interference of double-layer charging current or mass transport of species in the metal oxide. Instead, the high field model was used to simulate the potentiodynamic polarization curves of pure aluminum at 25, 50, 100, and 200 mV/s in neutral and acidic phosphate solutions, thus enabling quantitative analysis of local corrosion kinetics by fitting the potentiodynamic polarization curve.

Cell-free chitosan/silk fibroin/bioactive glass scaffolds with radial pore for in situ inductive regeneration of critical-size bone defects.

Tissue-engineered is an effective method for repairing critical-size bone defects. The application of bioactive scaffold provides artificial matrix and suitable microenvironment for cell recruitment and extracellular matrix deposition, which can effectively accelerate the process of tissue regeneration. Among various scaffold properties, appropriate pore structure and distribution have been proven to play a crucial role in inducing cell infiltration differentiation and in-situ tissue regeneration. In this study, a chitosan (CS) /silk fibroin (SF) /bioactive glass (BG) composite scaffold with distinctive radially oriented pore structure was constructed. The composite scaffolds had stable physical and chemical properties, a unique pore structure of radial arrangement from the center to the periphery and excellent mechanical properties. In vitro biological studies indicated that the CS/SF/BG scaffold could promote osteogenic differentiation of bone marrow mesenchymal stem cells (BMSCs) and the expression of related genes due to the wide range of connected pore structures and released active elements. Furthermore, in vivo study showed CS/SF/BG scaffold with radial pores was more conducive to the repair of skull defects in rats with accelerated healing speed during the bone tissue remodeling process. These results demonstrated the developed CS/SF/BG scaffold would be a promising therapeutic strategy for the repair of bone defects regeneration.

Cross-Linking Methods of the Silk Protein Hydrogel in Oral and Craniomaxillofacial Tissue Regeneration.

BACKGROUND: Craniomaxillofacial tissue defects are clinical defects involving craniomaxillofacial and oral soft and hard tissues. They are characterized by defect-shaped irregularities, bacterial and inflammatory environments, and the need for functional recovery. Conventional clinical treatments are currently unable to achieve regeneration of high-quality oral craniomaxillofacial tissue. As a natural biomaterial, silk fibroin (SF) has been widely studied in biomedicine and has broad prospects for use in tissue regeneration. Hydrogels made of SF showed excellent water retention, biocompatibility, safety and the ability to combine with other materials. METHODS: To gain an in-depth understanding of the current development of SF, this article reviews the structure, preparation and application prospects in oral and craniomaxillofacial tissue regenerative medicine. It first briefly introduces the structure of SF and then summarizes the principles, advantages and disadvantages of the different cross-linking methods (physical cross-linking, chemical cross-linking and double network structure) of SF. Finally, the existing research on the use of SF in tissue engineering and the prospects of using SF with different cross-linking methods in oral and craniomaxillofacial tissue regeneration are also discussed. CONCLUSIONS: This review is intended to show the advantages of SF hydrogels in tissue engineering and provides theoretical support for establishing novel and viable silk protein hydrogels for regeneration.

Correlating Corrosion to Surface Grain Orientations of Polycrystalline Aluminum Alloy by Scanning Electrochemical Cell Microscopy.

The study of grain-dependent corrosion behaviors of practical polycrystalline metals remains challenging due to the difficulty in eliminating the influences of other microstructural features, such as intermetallic particles and grain boundaries. In this work, we performed thousands of microscopic potentiodynamic polarization measurements on a polycrystalline aluminum alloy AA7075-T73 using the spatially resolved oil-immersed scanning electrochemical cell microscopy measurement. Data were extracted only from grain interior areas excluding intermetallic particles and grain boundaries. Based on the multiple potentiodynamic polarization measurements, the differences between grains can be revealed. Cathodic currents exhibited a strong grain orientation dependence with a decreasing order of {101} > {001} > {111}, agreeing with the prediction from the order of atomic planar density. By contrast, the dependence of anodic currents on grain orientation was weak, and pitting was independent of grain orientation, which could be due to the limited mass transport of ions within the surface oxide film. This work highlights the capability of oil-immersed scanning electrochemical cell microscopy in resolving small electrochemical differences, which will greatly promote the study of grain-dependent behaviors of practical polycrystalline samples.

Controlling Surface Contact, Oxygen Transport, and Pitting of Surface Oxide via Single-Channel Scanning Electrochemical Cell Microscopy.

In single-channel scanning electrochemical cell microscopy, the applied potential during the approach of a micropipette to the substrate generates a transient current upon droplet contact with the substrate. Once the transient current exceeds a set threshold, the micropipette is automatically halted. Currently, the effect of the approach potential on the subsequent electrochemical measurements, such as the open-circuit potential and potentiodynamic polarization, is considered to be inconsequential. Herein, we demonstrate that the applied approach potential does impact the extent of probe-to-substrate interaction and subsequent microscale electrochemical measurements on aluminum alloy AA7075-T73.

Ag+ Interference from Ag/AgCl Wire Quasi-Reference Counter Electrode Inducing Corrosion Potential Shift in an Oil-Immersed Scanning Micropipette Contact Method Measurement.

Quantitative scanning micropipette contact method measurements are subject to the deleterious effects of reference electrode interference. The commonly used Ag/AgCl wire quasi-reference counter electrode in the miniaturized electrochemical cell of the scanning micropipette contact method was found to leak Ag+ into the electrolyte solution. The reduction of these Ag+ species at the working electrode surface generates a faradaic current, which significantly affects the low magnitude currents inherently measured in the scanning micropipette contact method. We demonstrate that, during the microscopic corrosion investigation of the AA7075-T73 alloy using the oil-immersed scanning micropipette contact method, the cathodic current was increased by the Ag+ reduction, resulting in positive shifts of corrosion potentials. The use of a leak-free Ag/AgCl electrode or an extended distance between the Ag/AgCl wire and micropipette tip droplet eliminated the Ag+ contamination, making it possible to measure accurate corrosion potentials during the oil-immersed scanning micropipette contact method measurements.

Oil-Immersed Scanning Micropipette Contact Method Enabling Long-term Corrosion Mapping.

This work reports the development of an oil-immersed scanning micropipette contact method, a variant of the scanning micropipette contact method, where a thin layer of oil wets the investigated substrate. The oil-immersed scanning micropipette contact method significantly increases the droplet stability, allowing for prolonged mapping and the use of highly evaporative saline solutions regardless of ambient humidity levels. This systematic mapping technique was used to conduct a detailed investigation of localized corrosion taking place at the surface of an AA7075-T73 aluminum alloy in a 3.5 wt % NaCl electrolyte solution, which is typically challenging in the conventional scanning micropipette contact method. Maps of corrosion potentials and corrosion currents extracted from potentiodynamic polarization curves showed good correlations with the chemical composition of surface features and known galvanic interactions at the microscale level. This demonstrates the viability of the oil-immersed scanning micropipette contact method and opens up the avenue to mechanistic corrosion investigations at the microscale level using aqueous solutions that are prone to evaporation under noncontrolled humidity levels.

Analysis and Identification of Golden pompano (Trachinotus blochii) Head Phospholipid Molecular Species by Liquid Chromatography-Mass Spectrometry.

In this study, we first isolate phospholipid (PL) from Golden pompano head (GPH), and elucidate its structure. Gas chromatography (GC) was used to assess the GPH-PL fatty acid composition, Fourier transform infrared spectroscopy (FTIR) and ultraviolet absorption spectrometry (UV) were used for the qualitative analysis of GPH-PL, and LC-MS analysis was used to determine the major PL species. The results show that the contents of the various molecular species of GPH-PL were generally in the order phosphatidylcholine (PC) > sphingomyelin (SM) > lysophosphatidylcholine (LPC) > phosphatidylethanolamine (PE). The main molecular PC species are 16:0/18:2, 13:0/23:2, 27:2/9:0, 16:0/18:1, 12:0/22:2, 18:0/18:1, 18:0/24:1, and 18:1/24:0. The major SM species are 16:1/16:0, 16:0/18:1, 16:0/18:2, 16:0/26:2, and 18:1/24:1. The major LPC species are 18:1 and 16:0. The major PE species are 18:0/18:1 and 16:0/22:6. The total eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) contents in the GPH-PLs were 18.39%, and the content of DHA in the PL fraction was 16.47%. These results suggest that PLs from GPH is rich in polyunsaturated fatty acids (PUFA), which have good activity in anti-inflammation, anti-tumor, anti-osteoporosis and other aspects, and have important development prospects in the future.

Mass Spectrometric and Spectrophotometric Analyses Reveal an Alternative Structure and a New Formation Mechanism for Melanin.

In this study, we investigated the formation mechanism and chemical structure of melanin that results from the self-assembly of L-3,4-dihydroxyphenylalanine (L-DOPA). Using a combination of "top-down" and "bottom-up" approaches, and on the basis of state-of-the-art electrospray ionization mass spectrometry (ESI-MS) results, we propose a new formation mechanism and an alternative structure for melanin. Specifically, our study of the self-aggregation of L-DOPA based on L-DOPA clusters revealed that melanin is comprised partially of noncovalent supramolecular aggregate that is formed by self-aggregation of L-DOPA and with the individual monomers linked together by a combination of hydrogen bonds, π-π stacking, and ionic bonds. Furthermore, our study showed that unmodified L-DOPA may be part of the building block for melanin in addition to the previously proposed indole derivative based on L-DOPA cyclization. A similar self-aggregation phenomenon was also observed in other structurally related catecholamines, for example, adrenaline.