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We report an ultra-high-vacuum low-temperature (4.6 K) scanning tunneling microscopy study of the molecular structure and dynamics of a carbon monoxide (CO) monolayer adsorbed at 20 K on Cu(111). We observe the well-known 1.4 × 1.4 phase of CO/Cu(111) for the first time in real-space imaging. At 4.6 K, the hexagonal symmetry of the monolayer is locally broken by the formation of stripes made of single and double CO rows of different apparent heights. Using density functional theory calculations, we assign the high rows to CO molecules adsorbed mostly at off-center top sites and the low rows to bridge sites. Groups of three or four very high molecules appear randomly and are assigned to nearest-neighbor, titled top site molecules. We observe simultaneous hopping of a few CO molecules between adjacent top and bridge sites, which produces the apparent motion of the stripe pattern.Photolabile moieties have been utilized in applications ranging from peptide synthesis and controlled protein activation to tunable and dynamic materials. The photochromic properties of nitrobenzyl (NB) based linkers are readily tuned to respond to cytocompatible light doses and are widely utilized in cell culture and other biological applications. While widely utilized, little is known about how the microenvironment, particularly confined aqueous environments (e.g., hydrogels), affects both the mode and rate of cleavage of NB moieties, leading to unpredictable limitations in control over system properties (e.g., rapid hydrolysis or slow photolysis). To address these challenges, we synthesized and characterized the photolysis and hydrolysis of NB moieties containing different labile bonds (i.e., ester, amide, carbonate, or carbamate) that served as labile crosslinks within step-growth hydrogels. We observed that NB ester bond exhibited significant rates of both photolysis and hydrolysis, whereas, importantly, the NB carbamate bond had superior light responsiveness and resistance to hydrolysis within the hydrogel microenvironment. Exploiting this synergy and orthogonality of photolytic and hydrolytic degradation, we designed concentric cylinder hydrogels loaded with different cargoes (e.g., model protein with different fluorophores) for either combinatorial or sequential release, respectively. Overall, this work provides new facile chemical approaches for tuning the degradability of NB linkers and an innovative strategy for the construction of multimodal degradable hydrogels, which can be utilized to guide the design of not only tunable materials platforms but also controlled synthetic protocols or surface modification strategies.This study evaluated the applicability of a rapid analytical method using a headspace solid-phase microextraction gas chromatography/mass spectrometry (HS-SPME-GC/MS) technique to identify gamma-irradiated soybeans (0.1-5 kGy). From the partial least squares discriminant analysis used to discriminate between non-irradiated and irradiated soybean samples, 1,7-hexadecadiene was selected as the identifying marker. Response surface methodology experiments were used to determine the optimal HS-SPME extraction conditions including a carboxen/polydimethylsiloxane fiber with an extraction temperature of 98 °C and an extraction time of 55 min. HG106 1,7-Hexdecadiene was detected in all samples irradiated at ≥ 0.1 kGy under the optimized HS-SPME-GC/MS conditions, and the unique presence of the marker in a gamma-irradiated sample was verified by comparing the results from heat, steam, microwave, sonication, and ultraviolet treatments. The comparisons of the identification properties for various conventional methods validated several advances in HS-SPME-GC/MS analysis in terms of rapid analysis, high sensitivity, and absence of solvent.Increasing level of inflammation and oxidative stress could lead to memory impairment. The purpose of this study was to determine the neuroprotective effects of walnut peptides against memory deficits induced by lipopolysaccharide (LPS) in mice and further to explore the underlying anti-inflammatory mechanisms against LPS-elicited inflammation in BV-2 cells. Results showed that walnut protein hydrolysate (WPH) and its low-molecular-weight fraction (WPHL) could ameliorate the memory deficits induced by LPS via normalizing the inflammatory response and oxidative stress in brain, especially WPHL. Furthermore, 18 peptides with anti-inflammatory activities on LPS-activated BV-2 cells were identified from WPHL and it was found that Trp, Gly, and Leu residues in peptides might contribute to the anti-inflammation. Meanwhile, the strong anti-inflammatory effects of LPF, GVYY, and APTLW might be related to their hydrophobic and aromatic amino acid residues as well. LPF, GVYY, and APTLW could reduce the content of proinflammatory mediators and cytokines by downregulating related enzyme expressions and mRNA expressions. Additionally, ROS and mitochondria homeostasis might also contribute to their anti-inflammatory effects.We outline a method by which the surface preference of a species in a multicomponent mixture may be obtained using surface-specific visible-infrared sum frequency generation (SFG) spectroscopy combined with bulk infrared absorption and/or Raman data. In general, the problem is complicated by the fact that the SFG signal is a function of both the surface coverage and the structure of the molecules. Two-dimensional correlation analysis can be used to reveal which spectral features are changing synchronously, that is, in phase with each other, and which ones are evolving in a manner that is phase-shifted by 90° (asynchronous correlation) as a function of the bulk composition. We provide a framework for determining the surface preference from the correlations between the vibrational modes in the SFG spectra and between the modes from SFG and bulk infrared and/or Raman spectra. When compared to the equivalent analysis performed using the SFG spectra alone, this method can be used with the data obtained using a single-beam polarization and in congested spectral regions where fitting to isolate the behavior of individual vibrational modes is not robust.

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