α-Alkylation and Asymmetric Transfer Hydrogenation of Tetralone via Hydrogen Borrowing and Dynamic Kinetic Resolution Strategy Using a Single Iridium(III) Complex.

Here we present a novel strategy for the synthesis of enantiomerically enriched tetrahydronaphthalen-1-ols. The reaction proceeds via an alkylation (via hydrogen borrowing) and ammonium formate-mediated asymmetric transfer hydrogenation (via dynamic kinetic resolution), giving alkylated tetralols in high yields and good enantio- and diastereoselectivity across a diverse range of both alcohol and tetralone substrates. Additionally, these products were successfully derivatized to several complex molecules, demonstrating the utility of the tetrahydronaphthalen-1-ol.

Enzymatic upcycling of wild-simulated ginseng leaves for enhancing biological activities and compound K.

Compound K (CK), a ginsenoside with high bioavailability, is present at low levels in wild-simulated ginseng leaves (WSGL). WSGL contains the CK precursors, Rd and F2, in amounts up to 26.4 ± 0.4 and 24.1 ± 1.9 mg/g extract, respectively. In this study, CK production in WGSL reached 25.9 ± 1.0 mg/g extract following treatment with Viscozyme, Celluclast 1.5 L, Pectinex Ultra SP-L, and their combination. The antioxidant activities indicated by oxygen radical absorbance capacity, ferric reducing antioxidant power, and ABTS- and DPPH radical scavenging activity of enzyme-treated WSGL were enhanced 1.69-, 2.51-, 2.88-, and 1.80-fold, respectively, compared to non-treated WSGL. Furthermore, the CK-enriched WSGL demonstrated a 1.94-fold decrease in SA-ß-galactosidase expression in human dermal fibroblasts and a 3.8-fold enhancement of inhibition of nitric oxide release in lipopolysaccharide-induced RAW 264.7 cells relative to non-treated WSGL. Consequently, WSGL subjected to enzymatic upcycling has potential as a functional material in the food and pharmaceutical industries.

Immobilized Candida antarctica lipase B as an sn-1,3 regiospecific biocatalyst for the interesterification of triacylglycerols with fatty acid ethyl esters.

Candida antarctica lipase B (CALB) is regarded as non-regiospecific. This study aimed to investigate the regiospecificity of CALB in the solvent-free interesterification of high-oleic sunflower oil with stearic acid ethyl ester for 1,3-distearoyl-2-oleoylglycerol (SOS)-rich fat preparation using a packed bed reactor. The content ratio of 1,2-distearoyl-3-oleoylglycerol (SSO) to SOS (denoted by SSO/SOS content) obtained using Lipozyme 435 (a commercially immobilized CALB; 0-4.1%), at residence times (1-32 min) was similar to that obtained using Lipozyme RM IM (0-3.0%), but lower than that obtained using Lipozyme TL IM (6.0-39.4%). When immobilized on Lewatit VP OC 1600, Lipozyme CALB had an SSO/SOS content of 0-10.4%, which was greater than that of Palatase 20,000 L (0-1.1%) but was lower than that of Lipozyme TL 100 L (8.8-97.7%). Our findings suggest that immobilized CALB shows distinct sn-1,3 regiospecificity in the interesterification of triacylglycerol with fatty acid ethyl esters.

Electrodeposited reduced graphene oxide-PEDOT:PSS/Nafion hybrid interface for the simultaneous determination of dopamine and serotonin.

The electrochemically deposited reduced graphene oxide-PEDOT:PSS/Nafion (rGO-PP/NF) hybrid material has provided a favorable interface for the simultaneous detection of dopamine (DA) and serotonin (5-HT). The rGO-PP/NF onto the Au seed layer of the flexible substrate was simple, and it was followed by the sequential electrophoretic deposition of GO, reduction at the optimal pH buffer media, electropolymerization of EDOT:PSS, and Nafion coating. The strong electron-transport capacity between rGO-PEDOT:PSS and the negatively charged Nafion matrix might allow the highly sensitive, simultaneous, and selective detection of DA and 5-HT due to its high affinity for cations. In the results of the electrochemical response, well-separated oxidation peaks were observed in a mixture that contained various concentrations of DA and 5-HT. It showed the dynamic sensing of DA and 5-HT in the ranges of 0.5-75 µM and 0.05-50 µM, respectively, and the detection limits of 0.17 and 0.16 µM, respectively. In the mixture of DA and 5-HT, the sensor had a detection limit of 0.1 µM for 5-HT and DA, and its sensitivities of DA and 5-HT were 99.3 and 86 µA/µMcm2. Furthermore, it demonstrated high selectivity, reproducibility, stability, and a recovery property in the human serum spike test that was good enough for the practical use.

Turmeric extract (Curcuma longa L.) regulates hepatic toxicity in a single ethanol binge rat model.

Hepatic alcohol clearance is a key factor to overcome alcohol hangovers, and over the period, alcohol hangovers may lead to inflammation and oxidative stress. Natural food products with high antioxidant and anti-inflammatory effects might contribute to hepatic alcohol clearance, a hypothesis in this study. The present study aimed to evaluate the influence of turmeric (Curcuma longa L., Zingiberaceae) is an herbal product having antioxidant and anti-inflammatory activities, on alcohol metabolism using binge alcohol drinking rat model. In vivo investigations revealed that pretreatment with turmeric extract enhanced alcohol dehydrogenase (ADH) and aldehyde dehydrogenase (ALDH) activities upon binge ethanol (3 g/kg). Additionally, pretreatment with turmeric extract regulated CYP2E1 activity and levels of reactive oxygen species (ROS), Bax, Bcl-2, and inflammatory mediators like IL-1ß, IL-6, and TNF-α. Moreover, turmeric extract upregulated superoxide dismutase, catalase, and glutathione peroxidase activities in liver tissues. Together, these observations shed light on the potential beneficial effects of turmeric extract against acute liver toxicity. The results offer an alternative natural functional food product, turmeric extract, to prevent the negative implications of binge drinking.

Biochemical characterization of synthesized fisetin glucoside by dextransucrase from Leuconostoc mesenteroides NRRL B-1299CB4 with enhanced water solubility.

Fisetin (7,3',4'-flavon-3-ol) is a flavonol found in plants, fruits, and vegetables. It exhibits diverse biological activities, including antioxidant, anti-inflammatory, and anti-cancer effects. However, the low water solubility and bioavailability of fisetin restrict its pharmaceutical applications. In this work, we synthesized a novel fisetin-4'-O-α-D-glucopyranoside (FST-G1) using transglucosylation with sucrose, fisetin, and dextransucrase from Leuconostoc mesenteroides NRRL B-1299CB4. The water solubility of FST-G1 (109.8 ± 6.3 mg/L) was enhanced compared to fisetin (13.6 ± 1.3 mg/L). The antioxidant activities of FST-G1 in non-cellular assays, including ORAC, ABTS•+, and FRAP assays, were lower compared to fisetin. However, FST-G1 exhibited higher nitric oxide inhibition (62.5 µM; 92.3 %) in lipopolysaccharide-stimulated RAW 264.7 murine macrophage cells compared to fisetin (81.4 %). Anti-lipid accumulation in mouse 3T3-L1 cells treated with FST-G1 was similar to that in cells treated with fisetin. Taken together, the novel synthesized FST-G1 is expected to become a promising functional material for using in the pharmaceutical industry.

Development of GO/Co/Chitosan-Based Nano-Biosensor for Real-Time Detection of D-Glucose.

Electrochemical nano-biosensor systems are popular in the industrial field, along with evaluations of medical, agricultural, environmental and sports analysis, because they can simultaneously perform qualitative and quantitative analyses with high sensitivity. However, real-time detection using an electrochemical nano-biosensor is greatly affected by the surrounding environment with the performance of the electron transport materials. Therefore, many researchers are trying to find good factors for real-time detection. In this work, it was found that a composite composed of graphite oxide/cobalt/chitosan had strong stability and electron transfer capability and was applied to a bioelectrochemical nano-biosensor with high sensitivity and stability. As a mediator-modified electrode, the GO/Co/chitosan composite was electrically deposited onto an Au film electrode by covalent boding, while glucose oxidase as a receptor was immobilized on the end of the GO/Co/chitosan composite. It was confirmed that the electron transfer ability of the GO/Co/chitosan composite was excellent, as shown with power density analysis. In addition, the real-time detection of D-glucose could be successfully performed by the developed nano-biosensor with a high range of detected concentrations from 1.0 to 15.0 mM. Furthermore, the slope value composed of the current, per the concentration of D-glucose as a detection response, was significantly maintained even after 14 days.

Phytochemical properties and functional characteristics of wild turmeric (Curcuma aromatica) fermented with Rhizopus oligosporus.

This study investigated the effect of solid-state fermentation of wild turmeric (Curcuma aromatica) with Rhizopus oligosporus, a common fungus found in fermented soy tempeh, on phytochemical and biological properties. Ultra-performance liquid chromatography-tandem mass spectrometry showed that fermented wild turmeric has higher concentrations of curcumin, demethoxycurcumin, bisdemethoxycurcumin, phenolic compounds and total flavonoid-curcuminoid after fermentation for 1-, 3-, and 5-day relative to non-fermented turmeric. The l-carnitine content reached 242 µg g-1 extract after fermentation for 7-day. Wild turmeric had 1.47- and 2.25-fold increases in ORAC and FRAP, respectively, after 3-day fermentation. The inhibitory effects of fermented wild turmeric on lipid accumulation from 3T3-L1 cells, nitric oxide production from lipopolysaccharide-stimulated RAW264.7 murine macrophages, and melanin formation by B16F10 mouse melanoma cells with α-MSH increased 1.08-, 1.44-, and 1.52-fold, respectively, after 3-day fermentation. Based on these results, fermented wild turmeric product can be used as a functional ingredient in the cosmeceutical and nutraceutical industries.

Enhancement of the water solubility and antioxidant capacities of mangiferin by transglucosylation using a cyclodextrin glycosyltransferase.

This study aimed to enhance the water solubility and antioxidant properties of mangiferin by transglucosylation using cyclodextrin glycosyltransferase (CGTase) from Thermoanaerobacter sp. The highest mangiferin to mangiferin glucoside conversion yield achieved was 88.9% using 60 mU/mL CGTase, 25 mM mangiferin, and 10% starch (w/v), with incubation at 60 °C for 10 h. The product of transglucosylation was purified and its chemical structure was determined to be glucosyl-α-(1→4)-mangiferin (MGF-g1) using matrix-assisted laser desorption ionization time-of-flight mass spectrometry and nuclear magnetic resonance spectroscopy. The water solubility of MGF-g1 was 5,093 times higher than that of mangiferin. MGF-g1 exhibited 1.6-fold higher 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity, 1.24-fold higher oxygen radical antioxidant capacity, and 1.19-fold higher ferric reducing ability power, compared to mangiferin. Moreover, the cyclooxygenase-2 inhibitory activity (IC50) of mangiferin and MGF-g1 were 76.44 ± 11.7 µM and 59.74 ± 2.8 µM, respectively. Our results suggest that the novel MGF-g1 has potential applications as a functional material in the food and pharmaceutical industries.

Development and Validation of Simple Age-Adjusted Objectified Korean Triage and Acuity Scale for Adult Patients Visiting the Emergency Department.

PURPOSE: The study aimed to develop an objectified Korean Triage and Acuity Scale (OTAS) that can objectively and quickly classify severity, as well as a simple age-adjusted OTAS (S-OTAS) that reflects age and evaluate its usefulness. MATERIALS AND METHODS: A retrospective analysis was performed of all adult patients who had visited the emergency department at three teaching hospitals. Sex, systolic blood pressure, diastolic blood pressure, pulse rate, respiratory rate, body temperature, O2 saturation, and consciousness level were collected from medical records. The OTAS was developed with objective criterion and minimal OTAS level, and S-OTAS was developed by adding the age variable. For usefulness evaluation, the 30-day mortality, the rates of computed tomography scan and emergency procedures were compared between Korean Triage and Acuity Scale (KTAS) and OTAS. RESULTS: A total of 44402 patients were analyzed. For 30-day mortality, S-OTAS showed a higher area under the curve (AUC) compared to KTAS (0.751 vs. 0.812 for KTAS and S-OTAS, respectively, p<0.001). Regarding the rates of emergency procedures, AUC was significantly higher in S-OTAS, compared to KTAS (0.807 vs. 0.830, for KTAS and S-OTAS, respectively, p=0.013). CONCLUSION: S-OTAS showed comparative usefulness for adult patients visiting the emergency department as a triage tool compared to KTAS.

Energy-efficient glucose recovery from chestnut shell by optimization of NaOH pretreatment at room temperature and application to bioethanol production.

Biofuel policies are currently being implemented globally to reduce greenhouse gas emissions. The recent European regulation, Renewable Energy Directive (RED) II, states that renewable resources should be used as raw materials. In this study, chestnut shell (CNS), a food processing residue, was utilized as a feedstock for bioethanol production. Statistical optimization was performed to improve biomass-to-glucose conversion (BtG) from the CNS. In order to design an energy-efficient process, the pretreatment was fixed at room temperature in the numerical optimization. The optimal conditions derived from the predicted model are as follows: temperature of 25 °C, reaction time of 2.8 h, and NaOH concentration of 1.9% (w/w). Under optimal conditions, both predicted and experimental BtG were 31.0%, while BtG was approximately 3.3-fold improved compared to the control group (without pretreatment). The recovered glucose was utilized for bioethanol fermentation by Saccharomyces cerevisiae K35 and the ethanol yield was achieved to be 98%. Finally, according to the mass balance based on 1000 g CNS, glucose of 310 g can be recovered by the pretreatment; the bioethanol production was approximately 155 g. This strategy suggests a direction to utilize CNS as a potential feedstock for biorefinery through the design of an economical and energy-efficient pretreatment process by lowering the reaction temperature to room temperature.

Self-supervised driven consistency training for annotation efficient histopathology image analysis.

Training a neural network with a large labeled dataset is still a dominant paradigm in computational histopathology. However, obtaining such exhaustive manual annotations is often expensive, laborious, and prone to inter and intra-observer variability. While recent self-supervised and semi-supervised methods can alleviate this need by learning unsupervised feature representations, they still struggle to generalize well to downstream tasks when the number of labeled instances is small. In this work, we overcome this challenge by leveraging both task-agnostic and task-specific unlabeled data based on two novel strategies: (i) a self-supervised pretext task that harnesses the underlying multi-resolution contextual cues in histology whole-slide images to learn a powerful supervisory signal for unsupervised representation learning; (ii) a new teacher-student semi-supervised consistency paradigm that learns to effectively transfer the pretrained representations to downstream tasks based on prediction consistency with the task-specific unlabeled data. We carry out extensive validation experiments on three histopathology benchmark datasets across two classification and one regression based tasks, i.e., tumor metastasis detection, tissue type classification, and tumor cellularity quantification. Under limited-label data, the proposed method yields tangible improvements, which is close to or even outperforming other state-of-the-art self-supervised and supervised baselines. Furthermore, we empirically show that the idea of bootstrapping the self-supervised pretrained features is an effective way to improve the task-specific semi-supervised learning on standard benchmarks. Code and pretrained models are made available at: https://github.com/srinidhiPY/SSL_CR_Histo.

Rapid and concise quantification of mycelial growth by microscopic image intensity model and application to mass cultivation of fungi.

The microbial food fermentation industry requires real-time monitoring and accurate quantification of cells. However, filamentous fungi are difficult to quantify as they have complex cell types such as pellet, spores, and dispersed hyphae. In this study, numerous data of microscopic image intensity (MII) were used to develop a simple and accurate quantification method of Cordyceps mycelium. The dry cell weight (DCW) of the sample collected during the fermentation was measured. In addition, the intensity values were obtained through the ImageJ program after converting the microscopic images. The prediction model obtained by analyzing the correlation between MII and DCW was evaluated through a simple linear regression method and found to be statistically significant (R2 = 0.941, p < 0.001). In addition, validation with randomly selected samples showed significant accuracy, thus, this model is expected to be used as a valuable tool for predicting and quantifying fungal growth in various industries.

Flexible sensor with electrophoretic polymerized graphene oxide/PEDOT:PSS composite for voltammetric determination of dopamine concentration.

We demonstrate a novel, flexible sensor with graphene oxide/PEDOT:PSS (GO/PEDOT:PSS) composite for voltammetric determination of selective low levels of dopamine. The well-distributed GO and EDOT:PSS suspension in water were deposited simply and polymerized. Consequently, the EDOT:PSS provided a strong interaction between GO and PEDOT:PSS, and it also had well-tailored interfacial properties that allowed the highly selective and sensitive determination of DA. Since the interfacial net charge is well-constructed, the sensor satisfies both the requirements of selectivity and the highly sensitive detection of low amounts of DA. In the results, the sensor with the GO/PEDOT:PSS composite exhibited a low interfacial impedance of about 281.46 ± 30.95 Ω at 100 Hz and a high charge storage capacity (53.94 ± 1.08 µC/cm2) for the detection of dopamine. In addition, the interference from ascorbic acid was reduced effectively to a minimum by electrostatic charge repelling of the AA and the distinct difference for the oxidation peak of the UA. Due to the fact that the GO/PEDOT:PSS composite had a net negative charge and, enhanced interfacial properties, the sensor showed a dopamine detection limit of 0.008 µM and a sensitivity of 69.3 µA/µMcm2.

Selective Production of Bio-Based Linear Alpha-Olefin from Wasted Fatty Alcohol on Al2O3 for Bio-Based Chemicals.

The catalytic dehydration of a bio-based fatty alcohol was performed using Al2O3 prepared by solvothermal synthesis for selective production of long-chain linear-alpha-olefins (LAO). The effect of the synthesis temperature of alumina precursors on the dehydration of 1-octadecanol (C18H38O) was examined based on the textural properties and Lewis acid-base properties of the catalysts. Amorphous alumina synthesized at 325 °C showed the highest surface area (233.07 m2/g) and total pore volume (1.237 cm3/g) among the catalysts and the best dehydration results: 93% conversion, 62% selectivity of 1-octadecene (C18H36), and 89% LAO purity. This was attributed to the increased Al/O ratio and atomic concentration of surface O in alumina, which were important factors in the catalytic dehydration of 1-octadecanol through the synergistic catalysis of acid-base pairs. The produced bio-based LAO can be key intermediates for synthesis of oxo alcohols and poly-alpha-olefins, as alternatives to petroleum-based LAO to achieve carbon neutrality in chemical industry.

Preparation of Low-Diacylglycerol Cocoa Butter Equivalents by Hexane Fractionation of Palm Stearin and Shea Butter.

Herein, we prepared 1,3-dipalmitoyl-2-oleoyl glycerol (POP)-rich fats with reduced levels of diacylglycerols (DAGs), adversely affecting the tempering of chocolate, via two-step hexane fractionation of palm stearin. DAG content in the as-prepared fats was lower than that in POP-rich fats obtained by previously reported conventional two-step acetone fractionation. Cocoa butter equivalents (CBEs) were fabricated by blending the as-prepared fats with 1,3-distearoyl-2-oleoyl glycerol (SOS)-rich fats obtained by hexane fractionation of degummed shea butter. POP-rich fats achieved under the best conditions for the fractionation of palm stearin had a significantly lower DAG content (1.6 w/w%) than that in the counterpart (4.6 w/w%) prepared by the previously reported method. The CBEs fabricated by blending the POP- and SOS-rich fats in a weight ratio of 40:60 contained 63.7 w/w% total symmetric monounsaturated triacylglycerols, including 22.0 w/w% POP, 8.6 w/w% palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol, 33.1 w/w% SOS, and 1.3 w/w% DAGs, which was not substantially different from the DAG content in cocoa butter (1.1 w/w%). Based on the solid-fat content results, it was concluded that, when these CBEs were used for chocolate manufacture, they blended with cocoa butter at levels up to 40 w/w%, without distinctively altering the hardness and melting behavior of cocoa butter.

Enantioselective Iridium-Catalyzed Allylation of Nitroalkanes: Entry to ß-Stereogenic α-Quaternary Primary Amines.

The first systematic study of simple nitronate nucleophiles in iridium-catalyzed allylic alkylation is described. Using a tol-BINAP-modified π-allyliridium C,O-benzoate catalyst, α,α-disubstituted nitronates substitute racemic branched alkyl-substituted allylic acetates, thus providing entry to ß-stereogenic α-quaternary primary amines. DFT calculations reveal early transition states that render the reaction less sensitive to steric effects and distinct trans-effects of diastereomeric chiral-at-iridium π-allyl complexes that facilitate formation of congested tertiary-quaternary C-C bonds.

Improvement of Enzymatic Glucose Conversion from Chestnut Shells through Optimization of KOH Pretreatment.

Worldwide, about one-third of food produced for human consumption is wasted, which includes byproducts from food processing, with a significant portion of the waste still being landfilled. The aim of this study is to convert chestnut shells (CNSs) from food processing into a valuable resource through bioprocesses. Currently, one of the highest barriers to bioprocess commercialization is low conversion of sugar from biomass, and KOH pretreatment was suggested to improve enzymatic digestibility (ED) of CNS. KOH concentration of 3% (w/w) was determined as a suitable pretreatment solution by a fundamental experiment. The reaction factors including temperature, time and solid/liquid (S/L) ratio were optimized (77.1 g/L CNS loading at 75 °C for 2.8 h) by response surface methodology (RSM). In the statistical model, temperature and time showed a relatively significant effect on the glucan content (GC) and ED, but S/L ratio was not. GC and ED of the untreated CNS were 45.1% and 12.7%, respectively. On the other hand, GC and ED of pretreated CNS were 83.2% and 48.4%, respectively, and which were significantly improved by about 1.8-fold and 3.8-fold compared to the control group. The improved ED through the optimization is expected to contribute to increasing the value of byproducts generated in food processing.

Toxicity evaluation and biodegradation of phenanthrene by laccase from Trametes polyzona PBURU 12.

The newly isolated Trametes polyzona PBURU 12 demonstrated a high tolerance and potential for the degradation of phenanthrene. The fungal isolate was able to tolerate 100 ppm of phenanthrene with 45% relative growth. The crude laccase produced by Trametes polyzona PBURU 12 was able to degrade phenanthrene by up to 98% within 24 h. The degradation metabolites showed the absence of toxic compounds. Microbial viability tests using E. coli and B. subtilis revealed that the treated phenanthrene was less toxic than untreated phenanthrene. Phytotoxicity and genotoxicity tests, using Vigna radiata and Allium cepa, indicated that the treated phenanthrene was less toxic to the plants. No mutagenic activity was found in the Ames test. The crude laccase from Trametes polyzona PBURU 12 was demonstrated as a potential tool for the biodegradation of PAHs (phenanthrene), with low toxic effects after the degradation.