In this article, we describe a method of delivery of chondroitin sulfate to skin as nanoparticles and demonstrate its anti-inflammatory and antioxidant role using UV irradiation as a model condition. These nanoparticles, formed through electrostatic interactions of chondroitin sulfate with a skin-penetrating peptide, were found to be homogenous with positive surface charges and stable at physiological and acidic pH under certain conditions. They were able to enter into the human keratinocyte cell line (HaCaT), artificial skin membrane (mimicking the human skin), and mouse skin tissue unlike free chondroitin sulfate. The preapplication of nanoparticles also exhibited reduced levels of oxidative stress, cyclobutane pyrimidine dimer formation, TNF-α, and so on in UV-B-irradiated HaCaT cells. In an acute UV-B irradiation mouse model, their topical application resulted in reduced epidermal thickness and sunburn cells, unlike in the case of free chondroitin sulfate. Thus, a completely noninvasive method was used to deliver a bio-macromolecule into the skin without using injections or abrasive procedures.This work aimed to determine the formation over time of 3-methylbutanal and 3-methylbutan-1-ol recognized as malty during the manufacture of Raclette-type cheese and the fermention of reconstituted skim milk, and filter-sterilized MRS broth. Using dynamic headspace-vacuum transfer in trap extraction followed by gas chromatography coupled with mass spectrometry-olfactometry (DHS-VTT-GC-MS-O) as a screening method for the malty compounds, five compounds (2-methylpropanal, 2- and 3-methylbutanal, and 2- and 3-methylbutan-1-ol) were identified as potential compounds causing the malty aroma in starter culture development and Raclette-type cheeses. Focus on compounds having a predominant sensorial effect (3-methylbutanal and 3-methylbutan-1-ol), spikings of leucine, 13C-labeled leucine, α-ketoisocaproic acid, and α-ketoglutaric acid provided a better understanding of their formation pathway. This study highlighted the discrepancies in the formation of 3-methylbutanal and 3-methylbutan-1-ol between the growth media; namely, despite the presence of free leucine available in MRS and the addition of an excess, no increase of the target compounds was observed. The concentration of these compounds in MRS increased only when α-ketoglutaric acid or α-ketoisocaproic acid was added, and a preference for the pathway to α-hydroxyisocaproic acid instead of 3-methylbutanal was shown. In addition, a formation of 3-methylbutanal when the bacteria were not yet active was observed when spiking α-ketoisocaproic acid, which potentially indicates that this part of the metabolism could take place extracellularly. These results could potentially unveil other, not-yet-identified reactants, directly influencing the production of compounds responsible for the malty aroma in Raclette cheese.A simple and efficient method for the regioselective thiolation of p-quinone methides with sodium aryl/alkyl sulfinates has been established using an acid/phosphine-induced radical route under transition-metal-free conditions. A broad range of sodium aryl/alkyl sulfinates and p-quinone methides (p-QMs) are compatible for the reaction, giving the expected products with good to excellent yields. Control experiments were also performed to gain insights into the generation mechanism of thiyl radicals and hydrogen-atom transfer process. This protocol provides a safe and feasible way for the formation of carbon-sulfur bonds.Recurrent nasopharyngeal carcinoma (NPC) is the main cause of poor prognosis for NPC patients after chemo- and radiotherapies. Subsequent long-term follow-ups of post-treatment patients are crucial for the early discovery of tumor recurrence with timely intervention. Current clinical imaging methods based on tissue morphology encounter difficulties in differentiating recurrent tumors from post-treatment inflammation and fibrosis. In this work, we apply a unique fiberoptic Raman endoscopy technique to address the challenges for label-free follow-up surveying of post-treatment NPC patients and accurate detection of tumor recurrence. Significant Raman spectral differences can be observed among normal, NPC, and nonrecurring post-treatment patients. Raman endoscopy provides diagnostic accuracy of 100% for detecting recurrent NPC from early post-treatment inflammation and diagnostic accuracy of 98.21% for separating recurrent NPC from long-term post-treatment fibrosis. Further quantitative Raman modeling on in vivo nasopharyngeal tissue Raman data acquired unveils the changes of major tissue biochemicals (e.g., triolein, elastin, keratin, fibrillar collagen, and type IV collagen) associated with primary NPC and post-treatment recurrent NPC tissue compared to normal nasopharyngeal tissue. This work demonstrates that fiberoptic Raman endoscopy can be a clinically powerful diagnostic tool for rapid, label-free post-treatment surveying and recurrent tumor detection in NPC patients at the molecular level.Two terminal metal-oxide-metal devices based on niobium oxide thin films exhibit a wide range of non-linear electrical characteristics that have applications in hardware-based neuromorphic computing. In this study, we compare the threshold-switching and current-controlled negative differential resistance (NDR) characteristics of cross-point devices fabricated from undoped Nb2O5 and Ti-doped Nb2O5 and show that doping offers an effective means of engineering the device response for particular applications. find more In particular, doping is shown to improve the device reliability and to provide a means of tuning the threshold and hold voltages, the hysteresis window, and the magnitude of the negative differential resistance. Based on temperature-dependent current-voltage characteristics and lumped-element modelling, these effects are attributed to doping-induced reductions in the device resistance and its rate of change with temperature (i.e., the effective thermal activation energy for conduction). Significantly, these studies also show that a critical activation energy is required for devices to exhibit NDR, with doping providing an effective means of engineering the current-voltage characteristics. These results afford an improved understanding of the physical mechanisms responsible for threshold switching and provide new insights for designing devices for specific applications.