Top-down, bottom-up, and history-driven processing of multisensory attentional cues in intellectual disability: An experimental study in virtual reality.

Models of attention demonstrated the existence of top-down, bottom-up, and history-driven attentional mechanisms, controlled by partially segregated networks of brain areas. However, few studies have examined the specific deficits in those attentional mechanisms in intellectual disability within the same experimental setting. The aim of the current study was to specify the attentional deficits in intellectual disability in top-down, bottom-up, and history-driven processing of multisensory stimuli, and gain insight into effective attentional cues that could be utilized in cognitive training programs for intellectual disability. The performance of adults with mild to moderate intellectual disability (n = 20) was compared with that of typically developing controls (n = 20) in a virtual reality visual search task. The type of a spatial cue that could aid search performance was manipulated to be either endogenous or exogenous in different sensory modalities (visual, auditory, tactile). The results identified that attentional deficits in intellectual disability are overall more pronounced in top-down rather than in bottom-up processing, but with different magnitudes across cue types: The auditory or tactile endogenous cues were much less effective than the visual endogenous cue in the intellectual disability group. Moreover, the history-driven processing in intellectual disability was altered, such that a reversed priming effect was observed for immediate repetitions of the same cue type. These results suggest that the impact of intellectual disability on attentional processing is specific to attentional mechanisms and cue types, which has theoretical as well as practical implications for developing effective cognitive training programs for the target population.

Comprehensive Investigation of the Effects of Brewing Conditions in Sample Preparation of Green Tea Infusions.

Chemical and biological investigation of green tea has been generally performed while using different infusions that are prepared without consideration of the effects of sample preparation conditions. In this study, for the first time, the effects of green tea brewing conditions on the antioxidant activity and chemical profiles of metabolome and catechin compounds were examined at 60 °C and 95 °C for a period of 5-300 min. The antioxidant capacities of the tea infusions, which were assessed as per 2,2-diphenyl-1-picryl-hydrazyl hydrate (DPPH) radical scavenging activity, depended more on temperature than time. Metabolomics study that was based on ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UHPLC-QTOF/MS) revealed that the metabolic profiles, including 33 differential metabolites, were significantly changed by temperature and time, with the effects of time being more evident at 95 °C starting after 30 min. Infusions that were brewed at 95 °C for greater than 30 min yielded distinct profiles in the hierarchical clustering analysis. The quantification of eight catechins by UHPLC-QqQ/MS showed that the total catechin level peaked at 95 °C brewing at 10 min, after which the levels of four epi-forms of catechins decreased and those of four non-epi-forms increased, implying the epimerization of catechins over time. These results suggest that the brewing conditions for sample preparation of green tea should be put into careful consideration in studies where green tea extracts are applied as aqueous infusions.

Assessment of chemical equivalence in herbal materials using chromatographic fingerprints by combination of three similarity indices and three-dimensional kernel density estimation.

An intuitive and practical way to control chemical equivalence of secondary metabolites in herbal materials based on chromatographic fingerprints deserves a thorough discussion, yet it is relatively unexplored. For the first time, we propose a mixture of three similarity indices, the congruence coefficient, the average of the peak area ratios, and the larger value between the maximum peak area ratio and the reciprocal of the minimum peak area ratio, to make up for the weak points of some widely used similarity indices and to evaluate the chemical equivalence of two fingerprints from various perspectives. The three similarity values are fed into a three-dimensional kernel density estimation to determine the quality of herbal materials. This estimation enables precise detection of anomalies in the absence of prior quality determination experience. Forty Atractylodes samples similar in appearance and indiscriminately used for medical purposes were used to demonstrate the effectiveness of the developed approach. After a reference sample was postulated, a quality assessment of the 40 samples was performed using the three similarity values and the estimated kernel density. The samples that were judged by the developed approach to be of good quality were compared with those chosen by the most popular approach using decision criterion of a single similarity index. The benefits of the proposed approach were evident in that the qualified samples had the composition ratio and individual concentrations of multi-components closer to those of the reference in general, and their inter-sample deviation was significantly smaller.

Tirucallane Triterpenoids from the Stems and Stem Bark of Cornus walteri that Control Adipocyte and Osteoblast Differentiations.

Cornus walteri Wanger (Cornaceae) has been broadly used in traditional East Asian medicine for the treatment of various disorders, including skin inflammation and diarrhea. As part of our efforts to identify structurally and/or biologically new compounds from Korean medicinal plants, we have explored potentially new bioactive constituents from C. walteri. In the present study, seven triterpenoids (1⁻7) were isolated from C. walteri stems and stem bark. Compounds 1⁻3 were new tirucallane triterpenoids (cornusalterins N-P) and compounds 4⁻7 were isolated for the first time from C. walteri. The structures of the new compounds were determined based on 1D and 2D NMR spectroscopic data interpretations and HR-ESIMS, as well as a computational method coupled with a statistical procedure (DP4+). The regulatory effects of the isolated triterpenoids (1⁻7) on mesenchymal stem cell (MSC) differentiation to adipocytes and osteoblasts were examined in the C3H10T1/2 cell line. Although these compounds had little effect on MSC differentiation to osteoblasts, lipid droplet formation in adipocyte-differentiated MSCs decreased in the presence of the seven triterpenoids. Compounds 1 and 4 each had a relatively distinct correlation between dose and efficacy, showing adipogenesis suppression at higher concentrations. Our findings demonstrate that the active compounds 1 and 4 can exert beneficial effects in regulation of adipocyte differentiation.

Deep eutectic solvent-based valorization of spent coffee grounds.

Spent coffee grounds (SCGs) are viewed as a valuable resource for useful bioactive compounds, such as chlorogenic acids and flavonoids, and we suggest an eco-friendly and efficient valorization method. A series of choline chloride-based deep eutectic solvents (DESs) were tested as green extraction solvents for use with ultrasound-assisted extraction. Extraction efficiency was evaluated based on total phenolic content (TPC), total flavonoid content, total chlorogenic acids, and/or anti-oxidant activity. A binary DES named HC-6, which was composed of 1,6-hexanediol:choline chloride (molar ratio 7:1) was designed to produce the highest efficiency. Experimental conditions were screened and optimized for maximized efficiency using a two-level fractional factorial design and a central composite design, respectively. As a result, the proposed method presented significantly enhanced TPC and anti-oxidant activity. In addition, phenolic compounds could be easily recovered from extracts at high recovery yields (>90%) by adsorption chromatography.

One-step sample preparation for convenient examination of volatile monoterpenes and phenolic compounds in peppermint leaves using deep eutectic solvents.

Deep eutectic solvents (DESs) were investigated as an extraction medium for one-step sample preparation for chemical characterization of peppermint (Mentha piperita L.). Rather than applying discontinuous, time-consuming extraction methods to prepare two types of extracts, peppermint leaves were extracted efficiently into a DES, which was composed of choline chloride and d-(+)-glucose at a 5:2 molar ratio. The produced peppermint extracts contained volatile monoterpenes and phenolics at levels sufficient for direct chemical examination of peppermint leaves. The extracted monoterpenes in DES could be quantified via a newly developed method based on headspace solid-phase microextraction coupled to gas chromatography. The same extracts were also directly used to assess phenolics in terms of total phenolic content, total flavonoid content, and antioxidant activity. The proposed method allowed one-step sample preparation for extraction of volatile monoterpenes and phenolics of peppermint leaves and could be applied to various peppermint samples obtained from different origins.

Development and Validation of an Analytical Method Readily Applicable for Quality Control of Tabebuia impetiginosa (Taheebo) Ethanolic Extract.

The dried inner bark of Tabebuia impetiginosa, known as taheebo or red lapacho, has numerous beneficial effects on human health. This study presents the first simple and reliable quantitative method that could serve for the QC of taheebo. The method uses LC-UV spectroscopy to determine the veratric acid (VA; 3,4-dimethoxybenzoic acid) content of taheebo extracts (TEs). Sample preparation entailed the dissolution of TE in methanol (MeOH), facilitated by ultrasonic radiation for 10 min. The optimized conditions included chromatographic separation on an Agilent Eclipse Plus C18 column (4.6 × 150 mm, 5 µm) at 30°C. The mobile phase consisted of 1% acetic acid in water and MeOH, which was eluted under gradient mode at a flow rate of 1.0 mL/min. The detection wavelength was 254 nm. Using these conditions, VA was selectively resolved, and the entire chromatographic analysis time was 27 min. The method was linear in the range of 50-500 µg/mL (r2 = 0.9995), precise (≤3.97% RSD), and accurate (97.10-102.72%). The validated method was applied to three batches of TE samples, yielding an estimated VA content range of 14.92-15.58 mg/g. Thus, the proposed method could serve as an easy and practical method for the QC of TEs or related products containing TEs.

Migration of epoxidized soybean oil from polyvinyl chloride/polyvinylidene chloride food packaging wraps into food simulants.

Epoxidized soybean oil (ESBO) has been used in polyvinyl chloride (PVC)/polyvinylidene chloride (PVDC) food packaging cling film as a plasticizer and stabilizer. The aim of this study was to investigate the migration of ESBO from PVC/PVDC cling film, based on gas chromatography mass spectrometry (GC-MS). The specific migration of ESBO was evaluated using various food simulants (water, 4% acetic acid, 50% ethanol and n-heptane) for PVC and PVDC wrap products. ESBO did not migrate into water and 4% acetic acid for all the tested samples. However, it was released into 50% ethanol and n-heptane in several PVC/PVDC wraps, with maximum migration levels of 38.4 ± 0.7 and 37.4 ± 0.8 µg/mL, respectively. These results demonstrate that ESBO is capable of being released from PVC/PVDC wrap into amphiphilic/oily food and its migration should be regularly monitored.

Identification of Major Flavone C-Glycosides and Their Optimized Extraction from Cymbidium kanran Using Deep Eutectic Solvents.

Cymbidium kanran, an orchid exclusively distributed in Northeast Asia, has been highly valued as a decorative plant and traditional herbal medicine. Here, C. kanran extracts were prepared in 70% aqueous methanol using ultrasound-assisted extraction (UAE) and subjected to liquid chromatography-photodiode array detection and ultra-high performance liquid chromatography-quadrupole-time-of-flight-mass spectrometry analysis, which were used for quantitative and qualitative analysis, respectively. It was found that the extracts were rich in flavone C-glycosides including vicenin-2, vicenin-3, schaftoside, vitexin, and isovitexin. Ten deep eutectic solvents (DESs) were synthesized by combining choline chloride (hydrogen bond acceptor) with various polyols and diols (hydrogen bond donors) and were tested as a medium for the efficient production of extracts enriched with potentially bioactive flavone C-glycosides from C. kanran. A DES named ChCl:DPG, composed of choline chloride and dipropylene glycol at a 1:4 molar ratio, exhibited the best extraction yields. Then, the effects of extraction conditions on the extraction efficiency were investigated by response surface methodology. Lower water content in the extraction solvent and longer extraction time during UAE were desirable for higher extraction yields. Under the statistically optimized conditions, in which 100 mg of C. kanran powder were extracted in 0.53 mL of a mixture of ChCl:DPG and water (74:26, w/w) for 86 min, a total of 3.441 mg g-1 flavone C-glycosides including 1.933 mg g-1 vicenin-2 was obtained. This total yield was 196%, 131%, and 71% more than those obtained using 100% methanol, water, and 70% methanol, respectively.

Solid-phase extraction assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet to determine sildenafil and its analogues in dietary supplements.

A novel analytical method for the simultaneous determination of the concentration of sildenafil and its five analogues in dietary supplements using solid-phase extraction assisted reversed-phase dispersive liquid-liquid microextraction based on solidification of floating organic droplet combined with ion-pairing liquid chromatography with an ultraviolet detector was developed. Parameters that affect extraction efficiency were systematically investigated, including the type of solid-phase extraction cartridge, pH of the extraction environment, and the type and volume of extraction and dispersive solvent. The method linearity was in the range of 5.0-100 ng/mL for sildenafil, homosildenafil, udenafil, benzylsildenafil, and thiosildenafil and 10-100 ng/mL for acetildenafil. The coefficients of determination were ≥0.996 for all regression curves. The sensitivity values expressed as limit of detection were between 2.5 and 7.5 ng/mL. Furthermore, intraday and interday precisions expressed as relative standard deviations were less than 5.7 and 9.9%, respectively. The proposed method was successfully applied to the analysis of sildenafil and its five analogues in complex dietary supplements.

Monitoring heavy metals, residual agricultural chemicals and sulfites in traditional herbal decoctions.

BACKGROUND: Asian traditional herbal preparations are frequently considered for the contamination with undeclared toxic or hazardous substances. The aim of this study was to determine the toxic heavy metals, pesticides and sulfur dioxide in decoctions that is a common form of final utilization in Korea. METHODS: A total of 155 decoctions composed of multi-ingredient traditional herbs were randomly sampled from Seoul in Korea between 2013 and 2014. For each decoction, the concentrations of four heavy metals (arsenic, cadmium, lead and mercury), 33 pesticides and sulfur dioxide were analyzed using inductively coupled plasma mass spectrometry (ICP-MS), mercury analyzer, gas chromatography/nitrogen phosphorous detector (GC/NPD), gas chromatography/micro electron capture detector (GC/µECD), and Monier-Williams method respectively. RESULTS: One hundred fifty-two of One hundred fifty-five decoctions (98.1%) contained one of three heavy metals (96.1% for As, 97.4% for Cd, and 90.3% for Pb, 0.0% for Hg). Their average concentrations (77.0 ± 79.7 ug/kg for As, 20.4 ± 23.7 ug/kg for Cd, and 68.8 ± 76.5 ug/kg for Pb) were approximately 20% of the maximum allowable limits of vegetable or ginseng beverage described in the Korean Food Standard Codex while their 95th percentile concentrations were below than the guideline for them. None of 33 pesticides was detected in 155 decoction samples, and only one sample showed over limit of detection for residual sulfites. CONCLUSIONS: This study support that the contained status of toxic heavy metals, pesticides and sulfur dioxide in herbal decoctions are currently within safe level in Korea, and provide a reference data for the further studies focused on the safety herbal preparations.

A 1H NMR-based metabolomics approach to evaluate the geographical authenticity of herbal medicine and its application in building a model effectively assessing the mixing proportion of intentional admixtures: A case study of Panax ginseng: Metabolomics for the authenticity of herbal medicine.

Ginseng, the root of Panax ginseng has long been the subject of adulteration, especially regarding its origins. Here, 60 ginseng samples from Korea and China initially displayed similar genetic makeup when investigated by DNA-based technique with 23 chloroplast intergenic space regions. Hence, (1)H NMR-based metabolomics with orthogonal projections on the latent structure-discrimination analysis (OPLS-DA) were applied and successfully distinguished between samples from two countries using seven primary metabolites as discrimination markers. Furthermore, to recreate adulteration in reality, 21 mixed samples of numerous Korea/China ratios were tested with the newly built OPLS-DA model. The results showed satisfactory separation according to the proportion of mixing. Finally, a procedure for assessing mixing proportion of intentionally blended samples that achieved good predictability (adjusted R(2)=0.8343) was constructed, thus verifying its promising application to quality control of herbal foods by pointing out the possible mixing ratio of falsified samples.

UPLC-QTOFMS based metabolomics followed by stepwise partial least square-discriminant analysis (PLS-DA) explore the possible relation between the variations in secondary metabolites and the phylogenetic divergences of the genus Panax.

Phylogenetic and metabolomic approaches have long been employed to study evolutionary relationships among plants. Nonetheless, few studies have examined the difference in metabolites within a clade and between clades of the phylogenetic tree. We attempted to relate phylogenetic studies to metabolomics using stepwise partial least squares-discriminant analysis (PLS-DA) for the genus Panax. Samples were analyzed by ultra-performance liquid chromatography-quadrupole time of flight mass spectrometry (UPLC-QTOFMS) to obtain metabolite profiles. Initially, conventional principal component analysis was subsequently applied to the metabolomic data to show the limitations in relating the expression of metabolites to divisions in the phylogenetic tree. Thereafter, we introduced stepwise PLS-DA with optimized scaling methods, which were properly applied according to the branches of the phylogenetic tree of the four species. Our approach highlighted metabolites of interest by elucidating the directions and degrees of metabolic alterations in each clade of the phylogenetic tree. The results revealed the relationship between metabolic changes in the genus Panax and its species' evolutionary adaptations to different climates. We believe our method will be useful to help understand the metabolite-evolution relationship.

Tailoring and recycling of deep eutectic solvents as sustainable and efficient extraction media.

The present study demonstrates that deep eutectic solvents (DESs) with the highest extractability can be designed by combining effective DES components from screening diverse DESs. The extraction of polar ginseng saponins from white ginseng was used as a way to demonstrate the tuneability as well as recyclability of DESs. A newly designed ternary DES (GPS-5) composed of glycerol, l-proline, and sucrose at 9:4:1 was used as a sustainable and efficient extraction medium. Based on the anti-tumor activity on HCT-116 cancer cells, it was confirmed that GPS-5 was merely an extraction solvent with no influence of the bioactivity of the ginsenosides extracted. Excellent recovery of the extracted saponins was easily achieved through solid-phase extraction (SPE). Recycling of the DES was accomplished by simple freeze-drying of the washed solutions from the SPE. The extraction efficiencies of the DESs recycled once, twice, and thrice were 92%, 85%, and 83% of that of the freshly synthesized solvent.

Highly efficient extraction of anthocyanins from grape skin using deep eutectic solvents as green and tunable media.

Deep eutectic solvents (DESs) were investigated as tunable, environmentally benign, yet superior extraction media to enhance the extraction of anthocyanins from grape skin, which is usually discarded as waste. Ten DESs containing choline chloride as hydrogen bond acceptor combined with different hydrogen bond donors were screened for high extraction efficiencies based on the anthocyanin extraction yields. As a result, citric acid, D-(+)-maltose, and fructose were selected as the effective DES components, and the newly designed DES, CM-6 that is composed of citric acid and D-(+)-maltose at 4:1 molar ratio, exhibited significantly higher levels of anthocyanin extraction yields than conventional extraction solvents such as 80% aqueous methanol. The final extraction method was established based on the ultrasound-assisted extraction under conditions optimized using response surface methodology. Its extraction yields were double or even higher than those of conventional methods that are time-consuming and use volatile organic solvents. Our method is truly a green method for anthocyanin extraction with great extraction efficiency using a minimal amount of time and solvent. Moreover, this study suggested that grape skin, the by-products of grape juice processing, could serve as a valuable source for safe, natural colorants or antioxidants by use of the eco-friendly extraction solvent, CM-6.

Evaluation of four different analytical tools to determine the regional origin of Gastrodia elata and Rehmannia glutinosa on the basis of metabolomics study.

Chemical profiles of medicinal plants could be dissimilar depending on the cultivation environments, which may influence their therapeutic efficacy. Accordingly, the regional origin of the medicinal plants should be authenticated for correct evaluation of their medicinal and market values. Metabolomics has been found very useful for discriminating the origin of many plants. Choosing the adequate analytical tool can be an essential procedure because different chemical profiles with different detection ranges will be produced according to the choice. In this study, four analytical tools, Fourier transform near­infrared spectroscopy (FT-NIR), 1H-nuclear magnetic resonance spectroscopy (1H­NMR), liquid chromatography-mass spectrometry (LC-MS), and gas chromatography-mass spectroscopy (GC-MS) were applied in parallel to the same samples of two popular medicinal plants (Gastrodia elata and Rehmannia glutinosa) cultivated either in Korea or China. The classification abilities of four discriminant models for each plant were evaluated based on the misclassification rate and Q2 obtained from principal component analysis (PCA) and orthogonal projection to latent structures-discriminant analysis (OPLS­DA), respectively. 1H-NMR and LC-MS, which were the best techniques for G. elata and R. glutinosa, respectively, were generally preferable for origin discrimination over the others. Reasoned by integrating all the results, 1H-NMR is the most prominent technique for discriminating the origins of two plants. Nonetheless, this study suggests that preliminary screening is essential to determine the most suitable analytical tool and statistical method, which will ensure the dependability of metabolomics-based discrimination.

Large-scale fabrication of 2-D nanoporous graphene using a thin anodic aluminum oxide etching mask.

A large-scale nanoporous graphene (NPG) fabrication method via a thin anodic aluminum oxide (AAO) etching mask is presented in this paper. A thin AAO film is successfully transferred onto a hydrophobic graphene surface under no external force. The AAO film is completely stacked on the graphene due to the van der Waals force. The neck width of the NPG can be controlled ranging from 10 nm to 30 nm with different AAO pore widening times. Extension of the NPG structure is demonstrated on a centimeter scale up to 2 cm2. AAO and NPG structures are characterized using optical microscopy (OM), Raman spectroscopy and field-emission scanning electron microscopy (FE-SEM). A field effect transistor (FET) is realized by using NPG. Its electrical characteristics turn out to be different from that of pristine graphene, which is due to the periodic nanostructures. The proposed fabrication method could be adapted to a future graphene-based nano device.

Comparison of primary and secondary metabolites for suitability to discriminate the origins of Schisandra chinensis by GC/MS and LC/MS.

Discrimination of the origins of plants as traditional medicinal herbs or functional foods is important to accurately comprehend their therapeutic effects or to appropriately utilize their qualities because different environmental backgrounds can induce diverse metabolic changes. In the present study, the origins of the herbal medicine Schisandra chinensis were differentiated using two instrumental approaches, GC/MS and LC/MS. The acquired data were processed using various programs to detect metabolites and statistically examined to measure the suitability of the methods. The R(2)X value of the PCA analysis was used to examine the identified metabolites as potential discriminative markers. The identification of markers by primary metabolites using GC/MS analysis was advantageous because of its reproducibility and the use of a constructed database. However, LC/MS analysis using secondary metabolites provided a greater number of distinguishable variables and higher qualitative R(2)X values for the markers, which suggested that determination of the origins of the plants was more favourable using secondary metabolites.

A new application of charged aerosol detection in liquid chromatography for the simultaneous determination of polar and less polar ginsenosides in ginseng products.

INTRODUCTION: Conventional liquid chromatographic methods coupled with ultraviolet or evaporative light scattering detection are not sensitive enough to determine both polar and less polar ginsenosides at low concentrations. OBJECTIVE: To establish a liquid chromatography-charged aerosol detection method for the simultaneous determination of polar and less polar ginsenosides in a variety of ginseng products METHODS: Fourteen polar and less polar ginsenosides were extracted and concentrated by solid phase extraction. These were subsequently baseline-separated on a conventional reversed-phase C18 -column (250 mm × 4.6 mm, 5 µm) with a simple mobile phase consisting of water and acetonitrile. Components were then detected by means of charged aerosol detection. RESULTS: The method developed allowed the simultaneous determination of six polar ginsenosides (Rg1 , Re, Rb1 , Rc, Rb, Rd) and eight less polar ginsenosides (Rg6 , F4 , Rk3 , Rh4 , Rg3 (S), Rg3 (R), Rk1 , Rg5 ) in a single chromatographic run. Further, the method was linear (R(2) > 0.99), accurate (relative recoveries, 90-112%), and precise (intraday RSD < 5.7% and interday RSD < 10.6%) within the concentration range tested. The method sensitivity was measured in terms of the limit of detection, which ranged from 0.5 to 4.0 µg/mL. CONCLUSION: Concentrations of 14 ginsenosides were determined simultaneously in one homemade red ginseng and 13 commercial ginseng products of different types (liquid and solid samples), and results showed that ginsenoside content varied significantly among the samples tested. The method developed could serve as a useful analytical tool for the quality control of ginseng products.