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Various mixtures were prepared depending on the mixing ratio of Scutellaria baicalensis hot water extract (SB-HW), and Chrysanthemum morifolium ethanol extract (CM-E) and their anti-inflammatory activity were compared. Among them, SB-HW (80 μg/mL)/CM-E (120 μg/mL) or SB-HW (40 μg/mL)/CM-E (160 μg/mL) significantly inhibited LPS-stimulated NO and IL-6 levels in RAW 264.7 cells. The SB-HW (80 μg/mL)/CM-E (120 μg/mL) mixture, which was determined as active mixture, significantly reduced MUC5AC secretion in PMA and LPS-induced NCI-H292 cells. The active mixture also reduced the production of PGE2 and IL-8 in PMA-induced A549 cells. LC-MS/MS analysis showed that the active mixture was composed of high contents of flavone glycosides, such as baicalin and cynaroside. Western blot analysis indicated that the active mixture suppressed phosphorylation of ERK, JNK, and p38, associating with the inhibition of MAPK signaling. Taken together, our results suggest that the active mixture could be applied as a new anti-inflammatory herbal medicine.AbbreviationsJNK: c-Jun N-terminal kinases; COPD: chronic obstructive pulmonary disease; CM: Chrysanthemum morifolium; COX-2: cyclooxygenase-2; ERK: extracellular-signal-regulated kinase; IL-6: interleukin-6; IL-8: interleukin-8; IL-12: interleukin-12; LPS: lipopolysaccharide; MAPK: mitogen-activated protein kinase; NO: nitric oxide; NK- κB: nuclear factor kappa B; p38: p38 mitogen-activated protein kinases; PBS: phosphate buffered saline; PMA: phorbol-12-myristate-13-acetate; SB: Scutellaria baicalensis; PGE2: prostaglandin E2; TBST: Tris-buffered saline containing 0.1% Tween 20; TIC: total ion chromatogram; TNF-α: tumor necrosis factor-alpha

Lemon myrtle leaves were extracted with ethanol at different temperatures (25, 50, and 80 °C) and times (2, 4, 6, and 10 h) to examine the effect of extraction conditions on total polyphenol contents (TPC), total flavonoid contents (TFC), their antioxidant, anti-inflammatory activities, and amount of phenolic compounds. Under optimal extraction conditions (80 °C and 6 h), the values were 23.37%, 102.72 mg gallic acid equivalents (GAE/g dry basis), 23.37 mg rutin equivalents (RE/g dry basis), 83.31%, 60.13%, and 1.10% for yield, TPC, TFC, DPPH, ABTS radical scavenging activity, and reducing power, respectively. In addition, total amount of the phenolic compounds of extract was determined as 43.9 μg/g. The anti-inflammatory effect was determined in lipopolysaccharide-stimulated RAW 264.7 cells and inhibited the production of inflammatory mediators such as nitric oxide (NO). These results indicate that extracts of lemon myrtle leaves have potential as a valuable natural product with antioxidant and anti-inflammatory.

We’ve observed intense fluorescence from the surface of lead formate crystals when they are precipitated from a CH3NH3PbBr3 (MAPbBr3) perovskite precursor solution. The crystals exhibit emission in the range of 500–550 nm with a photoluminescence quantum yield (PLQY) of up to 70%. The fluorescence is stable in water and at elevated temperature without significant decrease in PLQY for months, conditions which instantly decompose MAPbBr3. Fluorescence occurred with the highest quantum efficiency of 70% at an optimal 1 : 0.3 molar ratio of methylammonium formate and lead bromide and decreased rapidly for other ratios. Fluorescence was quenched using other halides (Cl or I) or other cations (Cs, ethylammonium, propylammonium, etc.). Single crystal analysis indicates that the material possesses the lead formate structure with lattice parameters which are identical to pristine lead formate, however, analysis of the particles by EDX, XPS and fluorescence microscopy confirms the presence of Br and fluorescence emission on the particle surfaces. The observed material characteristics indicate that the emissive species consists of a mixed-valence surface layer of Pb coordinated to both Br and formate ligands.

Although Ginsenosides are a major physiological component of red ginseng (RG), some isolated ginsenosides are known to have cytotoxic activity. This study was intended to reduce cytotoxicity and promote anti-inflammatory activity of ginsenosides by mixing the crude ginsenosides (RG-CG) and polysaccharides (RG-CP). RG-CG-CM, fractionated from RG-CG, not only had higher anti-inflammatory activity than that of RG-CG at 100 μg/mL, but also showed increased cytotoxicity, while RG-CP-4P and RG-CP-8P, fractionated from RG-CP, showed no anti-inflammatory activity and cytotoxicity. To reduce the cytotoxicity without affecting the high anti-inflammatory activity of RG-CG-CM, RG-CG-CM and RG-CP-4P were mixed in a ratio of 2:8. The anti-inflammatory activity was significantly increased at a concentration of 75 μg/mL, while no cytotoxicity was observed. A combination of RG-CP and RG-CG effectively reduced the cytotoxicity and enhanced the anti-inflammatory activity of RG-CG, specifically RG-CG-CM fraction, providing scope for its industrial application.

Background: In our previous study, Hibiscus syriacus leaf tissue was successfully cultivated in an optimized callus culture system, and subsequently extracted with 70% ethanol to prepare H. syriacus callus extract (HCE). The previous study suggested that the callus culture is useful method for obtaining the anti-inflammatory ingredients from H. syriacus. Purpose: In the present study, we aimed to investigate the effect of HCE on the colorectal cancer (CRC) and its underlying mechanism of action using HT-29 cells and thymus-deficient mice bearing HT-29 xenografts. Methods: The cytotoxicity of HCE was investigated by MTT and colonies formation. The underling mechanism by which HCE regulates specific proteins in HT-29 cells was evaluated by the proteomic analysis. These putative proteins were validated using qRT-PCR and immunoblotting analyses. Subsequently, oral administration of HCE for 15 days further evaluating the anti-tumor activity by mRNA and protein expressions levels and tumor histopathology. Results: Results of cell viability and colony formation assays revealed a significant cytotoxic effect of HCE at doses below 100 μg/mL against HT-29 cells, but not against normal cells. Through differential protein expression analysis, signaling pathways underlying anti-CRC activity were predicted in HCE-treated HT-29 cells: Notch signaling, cholesterol biosynthesis, and AMPK signaling pathways. qRT-PCR and immunoblotting analyses indicated that the cytotoxic effect of HCE against HT-29 cells might be associated with the suppression of Notch signaling, which positively contributes to cholesterol biosynthesis. To our knowledge, this can be presented as the first study to demonstrate the detailed relationship between Notch signaling and cholesterol-AMPK signaling. Our in vivo result further corroborated the in vitro finding that 100 and 200 mg/kg HCE for 15 days exerts its anti-cancer effect via Notch signaling-mediated suppression of cholesterol synthesis without systemic toxicity. Conclusion: Our findings can serve as a starting point for developing the novel anti-CRC agent using HCE, as a targeted medicine acting on regulating Notch signaling and cholesterol synthesis.

The development of new amine solvents without the major drawbacks of conventional amines is crucial to industrial applications of CO2 capture. This paper presents a water-lean CO2 capture solvent having a low regeneration energy and low degradation. The water-lean solvent, K2Sol, is a sterically hindered diamine; because of the hindered amine site, K2Sol easily forms bicarbonate, resulting in a high absorption capacity. The minimum solvent regeneration energy is obtained using Gaussian process Bayesian optimization (GPBO) and bench-scale pilot plant experiments. GPBO finds the optimal solution using the input and output relationship of experiments; thus, expensive first-principle model construction can be avoided. According to the pilot plant experiment, the optimal regeneration energies of monoethanolamine (MEA) and K2Sol are 4.3 and 2.8 GJ/t CO2, respectively, indicating that K2Sol requires only 65% of the regeneration energy of MEA. Fewer than 30 experiments are required to find the optimal pilot plant operation for both the MEA and K2Sol experiments. We also describe the superior properties of K2Sol in terms of the CO2 loading, cyclic capacity, regeneration temperature, and degradation.

Imidazoliums are commonly used ionic liquid cations in electrolyte in dye-sensitized solar cells (DSSCs). Here, the size effects of imidazolium cations bearing the cyanoethyl group on DSSC performance have been systematically investigated by introducing the different alkyl chains (C1–C12), by which size control is allowed in a range of 9–20 A. The large cations slow down electron recombination and ion diffusion, but, unexpectedly, they suppress downward shift of TiO2 conduction band significantly affecting on electron injection process. While all the cations used in this work demonstrate a better power conversion efficiency than that for the common imidazolium analogue, the interplay among the key processes results in the best performance with the medium-sized cation C4 (11 A). This work paves a way for design of efficient electrolyte cations for photovoltaic devices.

The oxidative carbonylation of alcohols to prepare corresponding dialkyl carbonates was investigated using alkali metal methylselenite [MSeO2(OCH3)] and alkali metal selenites (M2SeO3, M = Li, Na, K, Cs) as catalysts. Of various alcohols tested, methanol and 2-methoxyethanol (MEG) are found to be highly reactive, affording corresponding dialkyl carbonates in yields of more than 30%, which are significantly higher than those achieved with Cu-based catalysts under similar reaction conditions. XRD and GC-Mass analysis of the spent catalyst recovered from the M2SeO3-catalyzed reaction of methanol revealed that M2SeO3 was converted into elemental selenium and MHCO3 along with the formation of several selenium-containing by-products including malodorous dimethyldiselenide, 1,2-dimethoxydiselane, and O,Se-dimethyl carbonoselenoate. On the contrary, the oxidative carbonylation of MEG with K2SeO3 was highly selective toward the formation of bis(2-methoxyethyl) carbonate (BMEC), without producing any selenium-containing by-products. A plausible mechanism for the MSeO2(OCH3)- and M2SeO3-catalyzed oxidative carbonylation of MEG was suggested on the basis of mechanistic and experimental results.

Purpose Early outcome prediction after suicidal hanging is challenging in comatose survivors. We analysed the early patterns of brain diffusion-weighted magnetic resonance imaging (DWI) abnormalities in comatose survivors after suicidal hanging. Methods After suicidal hanging, 18 comatose survivors were prospectively evaluated from January 2013 to December 2016. DWI was performed within 3 h after hanging in comatose survivors. We evaluated Utstein style variables and analysed abnormal spatial profile of signal intensity on DWI, brain apparent diffusion coefficient (ADC) values, and qualitative DWI scores to predict neurological outcomes. Results All hanging associated cardiac arrest (CA) patients demonstrated bad neurological outcomes; 80% of non-CA comatose patients experienced good neurological outcomes. In hanging survivors with CA, cortical grey matter structures and deep grey nuclei exhibited profound ADC reductions and high DWI scores within 3 h after hanging, which was associated with diffuse anoxic brain damage with poor cerebral performance categories scores. CA comatose survivors had significantly lower ADC values and higher DWI scores compared to non-CA comatose survivors in the cortex and deep grey nuclei. Conclusion Although the presence of CA is the most important clinical prognosticator in hanging-associated comatose survivors, HSI abnormalities and low ADC values in the cortex and deep grey nuclei on DWI performed within 3 h after hanging are well-correlated with unfavourable outcomes regardless of therapeutic hypothermia. Therefore, early DWI may increase the sensitivity of poor outcome prediction and may be an effective combinatorial screening method when available prognostic variables are not reliable or conclusive.

In recent times, the development of functionalized nanoparticle methodology for biomedical applications has become a major challenge. In the present study, we prepared a novel gold nanoparticle (AuNP), named Curto-Cumin AuNP (CC-AuNP), using the biosynthetic process involving Nigella sativa (black cumin) seed extract and membrane vesicles isolated from the novel probiotic strain, Curtobacterium proimmune K3. Various spectrometric and microscopic analyses were performed to characterize the physicochemical properties of the nanoparticles. CC-AuNP exhibited significant cytotoxicity against human gastric adenocarcinoma (AGS) cells but not against normal cells. The toxic effects of the nanoparticles were associated with the excessive production of reactive oxygen species (ROS) in damaged mitochondria. Further, we investigated the molecular mechanisms underlying the cytotoxic effect of CC-AuNP. Results showed that except for B cell lymphoma 2 (Bcl-2), the intracellular apoptotic signaling molecules, such as p53, Bcl-associated X protein (Bax), and Caspase 9/Caspase 3 were significantly upregulated in AGS cells. ROS production and alterations in mitochondrial membrane potential were observed in AGS cells treated with CC-AuNP. The activation of autophagy flux-related biomarkers, such as LC3b/a, Beclin-1, p62, and Caspase 8, was confirmed by qPCR and western blotting. Autophagy pathway was suppressed in CC-AuNP-treated AGS cells and could not proceed further to the mature state. This was confirmed by the evaluation of both apoptosis and autophagy signaling pathways using autophagy-induced AGS cells treated with rapamycin, a well-studied autophagy activator. Overall, our results showed that CC-AuNP upregulates apoptotic signaling and suppresses the autophagy-related signaling pathway, and thus has potential as an anticancer agent. To our knowledge, the present study is the first to demonstrate that CC-AuNP may serve as novel therapeutic agent against gastric cancer. Furthermore, our study provides preliminary data which can be used to develop novel anticancer candidates and understand their anticancer mechanisms, and seems to be a good starting point for the development of alternative medications based on CC-AuNP.

Most of the studies on common evening primrose (Oenothera biennis L.) are focused on its oils (isolated from seed, root, and stem tissues). We aimed to investigate the effect of the oral administration of OBS-E on the improvement of skin function in skin-damaged hairless mice exposed to excessive ultraviolet B (UVB) radiation owing to the preliminary in vitro findings regarding the antioxidant, anti-wrinkle, and skin moisturizing activities of OBS-E. OBS-E administration for 14 weeks did not significantly affect the body weight or clinical signs. Significant reductions were observed in wrinkle parameters (area, number, length, and depth, and metalloproteinase levels) in OBS-E-administered mice compared with those in UVB-irradiated control mice. OBS-E significantly increased skin elasticity and hyaluronic acid content, but it significantly decreased transepidermal water loss. Histomorphometrical analysis revealed that OBS-E significantly reduced the epidermal thickness, area of the collagen-occupied region, and number of microfolds and inflammatory and mast cells. These results demonstrate that OBS-E can effectively enhance skin functions in terms of ameliorating wrinkle formation, promoting skin-moisturization, enhancing skin barrier function, and inhibiting inflammatory reactions. The obtained results provide good starting point for the continuation in the process of developing new inner beauty products based on OBS-E.

Toward the standardization of common evening primrose (Oenothera biennis) sprout extract (OBS-E), we aimed to obtain indicator compounds and use a validated method. HPLC-UVD allowed simultaneous quantification of the indicator compounds quercetin-3-O-glucuronide and ellagic acid. The method was validated in terms of specificity, linearity, precision, accuracy, and limit of detection/limit of quantification (LOD/LOQ). High specificity and linearity was demonstrated, with correlation coefficients of 1.0000 for quercetin-3-O-glucuronide and 0.9998 for ellagic acid. The LOD/LOQ values were 0.486/1.472 &mu, g/mL for quercetin-3-O-glucuronide and 1.003/3.039 &mu, g/mL for ellagic acid. Intra-day and inter-day variability tests produced relative standard deviation for each compound of &lt, 2%, a generally accepted precision criterion. High recovery rate were also obtained, indicating accuracy validation. The OBS-E prepared using various concentrations of ethanol were then analyzed. The 50% ethanol extract had highest content of quercetin-3-O-glucuronide, whereas the 70% ethanol extract possessed the lowest. However, the ellagic acid content was highest in the 70% ethanol extract and lowest in the 90% ethanol extract. Thus, quercetin-3-O-glucuronide and ellagic acid can be used industrially as indicator compounds for O. biennis sprout products, and our validated method can be used to establish indicator compounds for other natural products.

The present study aimed to investigate the effect of Oenothera biennis sprout extract (OBS-E) on skin-function improvement in an in vitro system and to identify its pharmaceutically active components. OBS-E showed antioxidant ability in radical scavenging and reducing power assays, significantly inhibited matrix metalloproteinases-1 and -2, and increased the production of type I collagen, indicating its anti-wrinkle activity. Furthermore, OBS-E significantly increased the level of hyaluronic acid (HA) and the expression of moisturizing genes, such as hyaluronic acid synthase 2 (HAS2) and aquaporin 3 (AQP3), indicating it is effective in enhancing skin hydration. High-performance liquid chromatography (HPLC) and mass spectrometry (MS) analyses showed that OBS-E contained high levels of polyphenolic acids, such as gallic acid and ellagic acid, in addition to flavonoid glycosides, such as luteolin 7-glucuronide and quercetin 3-glucuronide. Our results suggest that these major phytochemicals are likely to play crucial roles in the expression of antioxidant, anti-wrinkle, and moisturizing activities of OBS-E.

Toward the standardization of O. biennis sprout extract (OBS-E), we aimed to obtain indicator compounds, using a validated method. HPLC-UVD allowed simultaneous quantification of indicator compounds quercetin 3-glucuronide and ellagic acid. The method was validated in terms of specificity, linearity, precision, accuracy, and limit of detection/limit of quantification (LOD/LOQ). High specificity and linearity was demonstrated, with correlation coefficients of 1.0000 for quercetin 3-glucuronide and 0.9998 for ellagic acid. The LOD/LOQ values were 0.486/1.472 μg/mL for quercetin 3-glucuronide and 1.003/3.039 μg/mL for ellagic acid. Intra-day and inter-day variability tests produced relative standard deviation for each compound of

Excessive exposure to ultraviolet B (UVB) radiation causes skin aging (a process known as photoaging). This study examined whether subchronic (14-week) oral administration of a novel hydrolyzed chicken sternal cartilage extract—comprising naturally-occurring primarily hydrolyzed type II collagen peptides, chondroitin sulfate and hyaluronic acid, extracted from a single source—could reduce signs associated with photoaging in hairless mice. Administration of the extract to UVB-irradiated mice led to significant increases in skin elasticity and hyaluronic acid content, compared with UVB-irradiated controls. Matrix metalloproteinase expression, transepidermal water loss, dermal inflammatory cells and wrinkles were all significantly reduced by administration of hydrolyzed chicken sternal cartilage extract. This study is the first to demonstrate that oral administration of this novel extract, containing a unique single-source complex of primarily hydrolyzed type II collagen (rather than the more widely studied type I form), chondroitin sulfate and hyaluronic acid, reduces UVB-induced photoaging in hairless mice.

In this study, we prepared palatinose-sucrose (PS) mixtures from sucrose by enzymatic bioconversion to improve the low sweetness of palatinose and to develop sweeteners that can lower blood sugar levels. We hypothesized that PS mixtures containing 30% or 50% palatinose might demonstrate improvement of hyperglycemia. The physiological changes in C57BL/6J mice fed with these concentrations of PS mixture were recorded. After feeding the mice the different diets for 5 weeks, the diet with a higher palatinose content was observed to have resulted in lower serum glucose levels. The expression levels of various genes and proteins related to hepatic lipogenesis and cholesterol homeostasis were measured. The diet containing the 50% PS mixture induced lower expression of HMGCR, CYP7A1, and PPARγ as compared to the diet containing the 30% PS mixture. In conclusion, the ingestion of palatinose resulted in lower lipid levels compared to that of sucrose; therefore, palatinose would be a good alternative to sucrose as a healthy sweetener. PRACTICAL APPLICATIONS: Palatinose (isomaltulose), along with tagatose, allulose, and allose, is a well-known sugar substitute. Many studies have reported that palatinose has various beneficial effects on postprandial glucose metabolism, such as glycemic index, fat accumulation, hyperglycemia, and hyperinsulinemia. Although there are many advantages, including desirable biological functions, palatinose has limitations as a complete alternative for sucrose because of higher production costs, lower solubility, and lower sweetness. Therefore, we aimed to investigate the possibility of developing a sucrose substitute by preparing PS mixtures bioconverted using α-glucosyltransferase from sucrose and to promote the industrial application of palatinose. Our results suggest that 50% palatinose syrup may be a new candidate as a sugar substitute for industrial application.

Platycodon grandiflorum seeds (PGSE) and P. grandiflorum root extracts (PGRE) were prepared and their effect on glucose uptake were evaluated in C2C12 myotubes. PGSE had significantly higher total phenolic and flavonoid contents than PGRE (P

Lithium halide-based molten salts (LiX-[BMIm]Br) synthesized from the reactions of lithium halides (LiX, X = Cl or Br) with 1-butyl-3-methylimidazolium bromide ([BMIm]Br), and their catalytic performances and corrosivities were tested for the coupling reactions of ethylene oxide with carbon dioxide to produce ethylene carbonate. The activity of a molten salt was influenced with the change of halide ion. At a fixed molar amount of LiX, the activity of LiX-[BMIm]Br increased with increasing molar ratio of LiX/[BMIm]Br up to 1–1.25, and then decreased thereafter. Fast atom bombardment mass spectral analysis of LiBr-[BMIm]Br, obtained by dissolving LiBr in [BMIm]Br in a 1:1 molar ratio, implies that [Li a X a +1]− are active species for the carboxylation of ethylene oxide with LiX-[BMIm]Br. The corrosion test toward carbon steel coupons demonstrates that all the Cl-containing molten salts are corrosive, whereas the salts without containing Cl− are non-corrosive under the carboxylation condition.

Encapsulated curcumin (ENCC) was prepared from a commercial curcuminoids complex and was evaluated for its intestinal permeability and hepatoprotective effects. Intestinal permeability was evaluated using a Caco-2 intestinal cell monolayer system and the non-everted gut sac method. The hepatoprotective effect was evaluated in experimental rats administered alcohol for 4 weeks. The intestinal permeability results suggested that encapsulation is a useful method for enhancing adsorption of curcumin via the intestinal epithelium. ENCC administration resulted in the significant reduction of various serum indicators. Notably, most of the indicators elevated by ethanol decreased below normal levels when rats were administered a high dose of ENCC. Oral administration of ENCC also augmented the activity of glutathione peroxidase in the liver, and both normal curcumin and ENCC significantly alleviated high levels of malondialdehyde. Our results demonstrate a significant hepatoprotective effect of ENCC in vivo owing to its ability to improve bioavailability of curcumin.

(1) Background: Nanotechnology is being widely applied for anticancer strategies with few side effects. Nanoparticles (NPs) prepared from natural extracts are promising candidates for cancer treatment because of their unique physicochemical characteristics. This study aimed to prepare gold nanoparticles (AuNPs) from Phyllanthus emblica fruit extract (PEFE) using Bifidobacterium animalis subsp. lactis (B. lactis) and to evaluate their anticancer activity against the human gastric adenocarcinoma cell-line (AGS). (2) Methods: The safety of microbial biosynthesis AuNPs (PEFE-AuNPs) was assessed by evaluating the cytotoxicity. The anticancer activity of PEFE-AuNPs was investigated in AGS cells in terms of apoptosis and autophagy. (3) Results: PEFE-AuNPs exhibited significant cytotoxicity against AGS cells but not against normal cells. The apoptosis induced by PEFE-AuNPs in AGS cells was associated with PTEN-induced kinase 1 (PINK1)-Parkin mediated reduction of mitochondrial membrane potential and activation of intracellular signaling apoptosis pathways. The anticancer activity of PEFE-AuNPs was associated with induction of apoptosis through inhibition of autophagy, downregulation of LC3-II/LC3-I and Beclin-1 expression, and upregulation of p62 expression in AGS cells. (4) Conclusions: This study is the first to demonstrate the anticancer activity of PEFE-AuNPs against AGS cells. Our results provide a good starting point for the development of new anticancer products based on gold nanoparticles of P. emblica fruit extract.

Persimmon (Diospyros kaki), a familiar and widespread fruit worldwide, is known to exhibit several physiological effects because of the presence of pharmacologically active compounds called phytochemicals. However, its high-molecular-weight compounds, particularly polysaccharides, have not been extensively studied. In this study, D. kaki extract (DK) was fractionated into low- and high-molecular-weight fractions (DK-L and DK-H, respectively) through ethanol fractionation, and their effects on antioxidant, anti-inflammatory, and antiwrinkle activities were investigated by an in vitro system. DK-H contained significantly higher contents of neutral sugar, uronic acid, and polyphenols compared to DK and DK-L. Furthermore, DK-H exhibited significantly improved pharmacological activities, such as antioxidant, anti-inflammatory, and antiwrinkle properties, compared to those of DK and DK-L, demonstrating that DK-H may play an important role in mediating the beneficial effects of persimmon. Sugar composition analysis and molecular characterization indicated that DK-H consisted of a galacturonic acid (GalA)-rich polysaccharide with a molecular weight of &gt, 345 kDa that mainly comprised GalA and small amounts of neutral sugar and polyphenol residues. These results suggest that the bioactive fraction DK-H is likely to be a GalA-rich pectic polysaccharide containing a small number of polyphenol residues, which may be a novel candidate in the pharmaceutical and cosmeceutical industries.

Diamine-anchored Merrifield resins ([DAMR]CH3SO3; DA = diamine, MR = Merrifield resin, X = Cl, CH3SO3, and (CF3SO2)2N), synthesized from the reactions of Merrifield resin with a tertiary diamine selected from N,N,N′N′-tetramethylethylenediamine (TMEDA), 1,4-dimethylpiperazine (DMP), and 1,4-diazabicyclo[2,2,2]octane (DABCO), were found to exhibit excellent performance as SO2 adsorbents under both hydrous and dry conditions. Under dry conditions, the molar SO2 adsorption capacity of [DAMR]X was greatly affected by the nucleophilicity of the anion but was rarely influenced by the type of diamine anchored on the cation. In contrast, under hydrous conditions, the SO2 adsorption and desorption behaviors on [DAMR]X were strongly affected by the basicity of the diamine on the cation, [DAMR]+. Spectroscopic and experimental results suggest that in the presence of water SO2 is adsorbed on [DAMR]X as a bisulfite species, and the formation and the stability of the bisulfite species increase with the increasing basic...

Paraprobiotics, which are inactivated microbial cells or cell fractions that can confer beneficial effects upon uses, have garnered attention. In this study, we investigated the paraprobiotic effect of Kimchi-derived Lactobacillus plantarum K8 on skin moisturizing activity in human keratinocyte. Four species of lactic acid bacteria were prepared into cell lysates under high pressure. L. plantarum K8 lysate induced outstanding hyaluronic acid production in HaCaT cells, compared with the lysates of L. lactis, L. sakei, and Streptococcus thermophilus. L. plantarum K8 lysate prepared under high pressure of 27,000 psi with three passage times was optimized for inducing hyaluronan production. Results of real-time PCR and western blotting analyses indicated that L. plantarum K8 lysate could enhance skin-moisturizing activity via upregulating hyaluronic acid synthase-2 and aquaporin-3 expression in HaCaT cells. Collectively, our results present preliminary data for utilizing L. plantarum K8 paraprobiotic as a functional ingredient in moisturizing products.

The aim of this study was to identify sleep-promoting substance from Polygonatum sibiricum rhizome extract (PSE) with the regulation of sleep architecture. PSE showed a decrease in sleep latency time and an increase in the sleeping time. In the electroencephalography analysis of rats, PSE (150 mg/kg) showed an increase of non-rapid eye movement by 38% and a decrease of rapid eye movement by 31% compared to the control. This sleep-promoting activity was found to be involved in the GABA(A)-BDZ receptor. The chemical structure of the pure compound was determined by the (1)H and (13)C nuclear magnetic resonance spectroscopy and gas chromatography mass spectrometry analysis; active compound was glyceryl-1-monolinoleate. The commercial standard glyceryl-1-monolinoleate showed a similar inhibitory concentration on [(3)H]-flumazenil binding to GABA(A)-BDZ receptors with final active fraction of PSE. The results indicate that glyceryl-1-monolinoleate is a major active compound responsible for the PSE-derived sleep promotion.

Synthesis of formamides from the catalytic carbonylation of amines with CO is of great interest due to their wide applications of formamides as synthetic intermediates and aprotic polar solvents. Up to now, the most commonly used catalysts are either expensive noble metal compounds or difficult-to-handle alkali metal alkoxides. We have found that a solid base, K3PO4 is a highly active and selective catalyst for the carbonylation of primary and cyclic secondary amines, producing corresponding formaldehydes in yields up to 99% at relatively mild conditions. Spectroscopic and quantum mechanical calculation results indicate that such high activity of K3PO4 is closely related to the strong hydrogen bonding ability of PO43− with the amino group of an amine, thereby enhancing the nucleophilicity of the amino group enough to interact with a neutral molecule, CO and mediating proton transfer from the amino group to the carbonyl group. Characterization of spent catalyst by FT-IR and XRD implies that small portion of K3PO4 is converted into less active K2HPO4 during the carbonylation reaction.

Triphylite-NaFePO4 is a cathode material for Na(+)-ion batteries, whereas its alternative polymorph maricite-NaFePO4 is not. These two different polymorphs exhibit widely different magnetic structures; the ordered magnetic structure of triphylite-NaFePO4 below ∼50 K is described by the propagation vector q1 = (0, 0, 0) with collinear spins, and that of maricite-NaFePO4 below ∼13 K is described by q2 = (1/2, 0, 1/2) with noncollinear spins. We probed the causes for these differences by calculating the spin exchange interactions of the two polymorphs and determining the preferred orientations of their high-spin Fe(2+) (d(6), S = 2) ions on the basis of density functional calculations. Our study shows that maricite-NaFePO4 is not spin-frustrated, which is also the case for triphylite-NaFePO4, that the ordered magnetic structure of triphylite-NaFePO4 is determined mainly by spin exchange, whereas that of maricite-NaFePO4 is determined by both spin exchange and magnetic anisotropy, and that the preferred spin orientations in the two polymorphs can be explained by perturbation theory using spin-orbit coupling as the perturbation.

Both DABCO (1,4-diazabicyclo[2.2.2]octane) and Merrifield resin-anchored DABCO ([p-DABCO]Cl), prepared from the reaction of DABCO and Merrifield resin, were found to exhibit high activities for the transesterification of dimethyl carbonate (DMC) with glycerol to produce glycerol carbonate (GLC). FT-IR and NMR spectroscopic results suggest that such a high transesterification activity of DABCO could be attributed to its superior ability to activate glycerol via a strong hydrogen bond formation between a hydroxyl group of glycerol and an amino group of DABCO. Meanwhile, the activation of glycerol by [p-DABCO]Cl proceeds mainly through the hydrogen bond interaction between a hydroxyl group or groups of glycerol and Cl− of [p-DABCO]Cl. The catalytic activity of [p-DABCO]Cl was maintained up to 5 reuses, demonstrating that [p-DABCO]Cl could be used as a recyclable heterogeneous catalyst.

Three kinds of lanthanum oxides (La2O3) were synthesized from different methods and used as a catalyst in the transesterification of dimethyl carbonate (DMC) with glycerol for the synthesis of glycerol carbonate (GLC). Lanthanum oxide synthesized using a surfactant (S-La) showed a much higher GLC yield of 89.9% compared to other lanthanum oxides synthesized by calcination (C-La) and precipitation (P-La) at the reaction conditions of 90 °C, DMC/glycerol = 2, and catalyst/glycerol = 5 wt %. The best catalyst was obtained when the surfactant/La weight ratio was 12. XRD study revealed that S-La has large amount of monoclinic and hexagonal La2O2CO3 phases, which are assumed as active sites of the catalyst for the reaction.

A facile and efficient one-pot procedure for the synthesis of ring hydrogenated carbamates from aromatic amine and alkylene carbonate under H 2 gas pressure has been developed using a heterogeneous catalyst system comprising ruthenium and alkali metal carbonates. The effects of temperature, H 2 pressure, catalyst (types of loaded metal and their supports), molar ratio of substrate/catalyst, and solvent were also investigated. Among the alkali metal carbonates, the sodium carbonate was found as best promoter for nucleophilic attack and ring-opening (NARO) reaction and thus increased the yield of ring hydrogenated carbamate up to 88% when using Ru/C as ring hydrogenation (RH) catalyst. This catalyst system could be reused at least five times without significant loss of activity, which makes this process cost-effective and eco-friendly.

Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United StatesReceived March 7, 2014, Accepted May 7, 2014Key Words : Chromium catalyst, Spin-crossover, Ethylene trimerization, Density functional theoryIndustrially important linear alpha-olefins are commonlyproduced by oligomerization of ethylene or by Fischer-Tropsch synthesis followed by purification. Biggest challengefor the linear alpha olefin industry is a Schultz-Flory di-stribution of products made by most of the processes.

Hydrolysis of ionic cellulose (IC), 1,3-dimethylimidazolium cellulose phosphite, which could be synthesized from cellulose and dimethylimidazolium methylphosphite ([Dmim][(OCH3)(H)PO2]) ionic liquid, was conducted for the synthesis of glucose. The reaction without catalysts at 150 °C for 12 h produced glucose with 14.6% yield. To increase the hydrolysis yield, various acid catalysts were used, in which the sulfonated active carbon (AC-SO3H) performed the best catalytic activity in the IC hydrolysis. In the presence of AC-SO3H, the yields of glucose reached 42.4% and 53.9% at the reaction condition of 150 °C for 12 h and 180 °C for 1.5 h, respectively; however the yield decreased with longer reaction time due to the degradation of glucose. Consecutive catalyst reuse experiments on the IC hydrolysis demonstrated the catalytic activity of AC-SO3H persisted at least through four successive uses.

Various forms of MgO were synthesized and used as catalysts in the transesterification of dimethyl carbonate (DMC) with glycerol for the synthesis of glycerol carbonate (GLC). MgO synthesized using a surfactant (a triblock copolymer of ethylene oxide/propylene oxide/ethylene oxide, known as Pluronic F127) showed a much higher GLC yield of 75.4% compared to other MgO catalysts synthesized without using a surfactant at reaction conditions of 90 °C, DMC/glycerol = 2, and catalyst/glycerol = 5 wt%. With an increase of the weight ratio of the surfactant/Mg precursor, the catalytic activity was increased. However, the activity did not change substantially when the surfactant/Mg precursor ratio was greater than 5. The high catalytic activity of MgO prepared with the surfactant (MgO–S) is attributed to the higher basic site concentration on the surface. This originated from low-coordination oxide ions at the corner sites (O 3c 2− ), as shown in the basic site titration and UV–diffuse reflectance analysis results. It is also noted that MgO–S could be easily recovered after the reaction and reused at least five times without serious catalyst deactivation.

Ru/C-catalyzed hydrogenation of m-xylylene diamine into 1,3-cyclohexanebis(methylamine) was greatly accelerated by the presence of LiNO3, NaNO2, or NaNO3. It was found that the effect of the nitrate salt was significantly affected by the size of cation. The promoting effect of the nitrate salt increased with the decrease of the cation size: LiNO3 ~ NaNO3 > KNO3 > CsNO3 >> [1-butyl-3-methylimidazolium]NO3. XRD analysis of the recovered catalysts after the hydrogenation reactions showed that LiNO3 and NaNO3 were completely transformed into LiOH and NaOH, respectively, along with the evolution of NH3, while KNO3 and CsNO3 remained unchanged.

K3PO4 was found to effectively catalyze the carboxylation of amines by CO2, producing corresponding 1,3-disubstituted ureas in high yields and selectivities. X-ray diffraction and FT-IR spectroscopic analysis of the solid mixture, recovered from the carboxylation of n-butylamine, revealed that K3PO4 was completely transformed into KH2PO4 and KHCO3. Mechanistic and computational studies suggested that the high activity of K3PO4 could be attributed to the synergy effect exerted by the co-presence of KHCO3 and KH2PO4, generated from the interaction of K3PO4 with CO2 and water.

The pathways for the CO2 absorption and desorption in an aqueous solution of a heavily hindered alkanolamine, 2-(t- butylamino)ethanol (TBAE) were elucidated by X-ray crystallographic and 13C NMR spectroscopic analysis. In the early stage of the CO2 absorption, the formation of carbonate species ([TBAEH]2CO3) was predominant along with the generation of small amounts of zwitterionic species. With the progress of the absorption, the carbonate species was rapidly transformed into bicarbonate species ([TBAEH]HCO3), and the amounts of the zwitterionic species increased gradually. During desorption at 2-elevated temperature in the absence of CO2, [TBAEH]HCO3 was found to transform into [TBAEH]2CO3, where CO3 interacts with two [TBAEH]+ via hydrogen bondings.

The reaction of CuCl2, SeO2, and cetyltrimethylammonium bromide (CTAB) under the CO pressure in methanol produce a black solid, which is identified as cupric diselenide, CuIISe2 using various spectroscopic analyses. Impregnation of 5 wt% of CuSe2 onto CeO2 resulted in much more enhanced catalytic activity due to the uniform and highly dispersed particle. The reductive carbonylation of nitrobenzene (NB) as a model substrate has been examined in the presence of the CuSe2/CeO2 as a single component heterogeneous catalyst, which is found to exhibit excellent catalytic activity for generating methyl-N-phenyl carbamate (MPC) in a highly selective fashion. The effects of various reaction parameters such as temperature, pressure, and reaction time have been investigated. A plausible reaction mechanism using this cheap heterogeneous catalyst is also presented, especially invoking the importance of CuSe2(μ-CO) species.

The performance of N-alkylpyridinium-based ionic liquids with a SCN anion (PyILs) was evaluated for the selective extraction of aromatics from aliphatic hydrocarbons. The aromatic extraction ability of PyILs was greatly enhanced by the presence of a methyl group on the pyridinium ring at the 3- or 4-position, whereas the solubility of the aromatics in the PyILs decreased with increasing the number of methyl groups on the benzene ring. The FT-IR studies revealed that the solubility of an aromatic compound in a PyIL is closely correlated with the degree of aromatic C-H bending frequency shift observed during the dissolution of the aromatic compound in the PyIL: the larger the shift, the higher the solubility. The computational calculations on the dispersion interactions between aromatics and PyILs demonstrated that the anion-aromatic interaction is much more important than the cation-aromatic interaction in determining the aromatic solubility in PyILs, and such anion-aromatic interaction can be enhanced by introducing a methyl group at the carbon atom of the pyridinium ring.

Tetramethylammonium-based molten salts bearing a β-amino acid anion (TMAAs) are synthesized through Michael addition reactions of amines with methyl acrylate followed by hydrolysis and subsequent neutralization by using aqueous tetramethylammonium hydroxide. The CO(2) capture performances of the TMAAs are evaluated and are shown to interact with CO(2) in a 1:1 mode in both water and alcohol. FTIR and (13)C NMR spectroscopic studies on the interactions of TMAAs with CO(2) indicate that the type of CO(2) adduct varies with the solvent used. When water is used as the solvent, a bicarbonate species is produced, whereas hydroxyethylcarbonate and methylcarbonate species are generated in ethylene glycol and methanol, respectively. Computational calculations show that the carboxylate groups of TMAAs contribute towards the formation and stabilization of 1:1 CO(2) adducts through hydrogen bonding interactions with the hydrogen atoms of the amino groups.

Decarboxylation of glycerol carbonate (GLC) to produce 2,3-epoxy-1-propanol (glycidol) was conducted using various kinds of ionic liquids (ILs) as catalysts. ILs bearing an anion with medium hydrogen-bond basicity such as NO3- and I− exhibited the higher glycidol yields than those having an anion with low or strong hydrogen-bond. FT-IR spectroscopic analysis shows that both GLC and glycidol interact with anions of ILs through their hydroxyl groups. It was possible to improve the yield of glycidol when a zinc salt with a medium Lewis acidity was co-present along with an IL. The yield of glycidol was greatly increased up to 98% when the decarboxylation was conducted in the presence of a high-boiling aprotic solvent. Computational calculations on the mechanism using 1-butyl-3-methylimidazolium nitrate as a catalyst revealed that the first step is the NO3--assisted ring-opening of GLC followed by the ring closure, resulting in the formation of a 3-membered ring intermediate species.

We recently isolated an immunostimulating polysaccharide (BLE-P-I), which possesses a large proportion of arabinoxylan, from young barley leaves. In the present study, to elucidate the structural details of BLE-P-I, it was fractionated into enzyme-resistant fraction (BLE-P-I-X1) and arabinoxylan-rich oligosaccharide fraction (BLE-P-I-X2) after endo-xylanase hydrolysis. Commercial wheat arabinoxylan was also fractionated into WAX-XI and WAX-X2 after the same treatment. BLE-P-I-X2 consisted of arabinose and xylose, including 11 types of neutral glycosidic linkages, whereas WAX-X2 had less, with 6 types of linkages. Mass spectrometric results indicated that WAX-X2 was composed of a xylan backbone bearing only arabinose. In contrast, BLE-P-I-X2 consisted of a xylan backbone with acetate, arabinose, galactose, glucuronic acid, and 4-O-methylglucuronic acid, resembling structural characteristics as glucuronoarabinoxylan. Macrophage-stimulatory activity showed that BLE-P-I-X2 has a role in the expression of the activity. These results indicate that the structural complexity of arabinoxylan seems to be responsible for the immunomodulatory activity in barley leaf.

The crude polysaccharide (KPV-0) isolated from Korean persimmon vinegar was fractionated using gel filtration chromatography to enhance the immunostimulatory activity and to identify the structural features of active fraction. Among three fractions, KPV-I obtained in a void volume, demonstrated the potent production of macrophage-stimulating mediators, including tumor necrosis factor-α, interleukin (IL)-6, IL-12, and nitric oxide. KPV-I showed a combined single peak with high molecular weight of 55,000Da by high performance size exclusion chromatography. Component sugar analysis revealed that KPV-I contained mainly of arabinose, mannose, galactose, rhamnose and galacturonic acid. Single radial gel diffusion assay using β-glucosyl Yariv reagent showed that KPV-I contained arabinogalactan protein with 13.7%. Methylation analysis indicated that KPV-I contained 21 kinds of neutral glycosidic linkages, which seemed to be composed three kinds of polysaccharide; that is a rhamnogalacturonan-I (65-70%) derived from persimmon as a raw material, a mannan (20-25%) derived from fermentation-associated microorganisms, and a linear glucans (less than 10%). In conclusion, polysaccharide isolated from persimmon vinegar could augment the macrophage stimulation, and a large amounts of RG-I polysaccharide derived from persimmon is likely a crucial role in expression of the activity in persimmon vinegar.