Ether Residues Research Articles

Safety and efficacy of hyaluronic acid injectable filler in the treatment of nasolabial fold wrinkle: a randomized, double-blind, self-controlled clinical trial

IntroductionThe injectable skin fillers available for soft tissue augmentation are constantly growing, providing esthetic surgeons with more options in the treatment of scars, lines, and wrinkles. Hyaluronic acid (HA)-derived injectable fillers are ideal to reduce the appearance of nasolabial folding. This study investigated the efficacy and safety of the commercially available HA filler from Maxigen Biotech Inc. (MBI-FD) in the treatment of nasolabial folds (NLFs).MethodsWe analyzed 1,4-butanediol diglycidyl ether (BDDE) residues and injection force test and observed the protein content in MBI-FD, and then was cultured in fibroblast L929 cells and examined for cytotoxicity. Finally, 95 healthy participants underwent dermal filler injection therapy to evaluate the efficacy and safety for 24 and 52 weeks, respectively.ResultsBDDE residues in MBI-FD was <0.125 µg/mL. MBI-FD was fitted using 27- and 30-G injection needles with an average pushing force of 14.30 ± 2.07 and 36.43 ± 3.11 N, respectively. Sodium hyaluronate protein in MBI-FD was 7.19 µg/g. The cell viabilities of 1× and 0.5× MBI-FD were 83.25% ± 3.58% and 82.23% ± 1.85%, respectively, indicating MBI-FD had no cytotoxicity, and decreased NLF wrinkles with no serious adverse events.ConclusionMBI-FD is an effective filler for tissue augmentation of the NLFs and may be a suitable candidate as an injectable dermal filler for tissue augmentation in humans in the future.

Anti-oxidant and Anticancerous Effect of Fomitopsis officinalis (Vill. ex Fr. Bond. et Sing) Mushroom on Hepatocellular Carcinoma Cells In Vitro through NF-kB Pathway.

Fomitopsis officinalis (Vill. ex Fr. Bond. et Sing) is a medicinal mushroom, commonly called 'Agarikon'; it has traditionally been used to treat cough and asthma in the Mongolian population. The objective of the study was to examine the significance of biological activity of F. officinalis and evaluation of the antioxidant activity and anticancer activity of six fractions of F. officinalis residues (Fo1-powder form dissolved in ethanol, Fo2-petroleum ether residue, Fo3-chloroformic, Fo4-ethylacetate, Fo5-buthanolic, and Fo6-waterethanolic) against hepatocellular carcinoma cells. We performed in vitro studies of cell proliferation and viability assay, annexin V-FITC/Propidium Iodide assay, and NF-kB signaling pathway by immunoblot analysis. Our findings revealed that all six fractions/extracts have antioxidant activity, and somehow, they exert anticancerous effects against cancer cells. In cancerous cell lines (HepG2 and LO2), Fo3 chloroformic extract promoted the cancer cell apoptosis and cell viability, activated G2/M-phase cell cycle, and selectively induced NF-kB proteins, revealing as a novel antitumor extract. This study reports that Fo3-chloroformic extract is rich in antitumor activity, which was previously not investigated in cancer. To develop the impact of F. officinalis among natural products to treat/prevent oxidative stress disorders or cancers, further examinations of F. officinalis are needed to develop new natural drugs to treat cancer. However, this study assessed only one extract, Fo3-chloroformic, which has a significant impact against cancer cell lines.

1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN)-based porous organic polymers for visible-light-driven organic transformations in water under aerobic oxidation

A series of hyper-crosslinked POPs were constructed by Friedel–Crafts alkylation reaction of 4CzIPN with FDA, which contains a certain quantity of hydrophilic ether residues to facilitate visible-light-promoted aqueous organic transformations.

Self-assembly involving hydrogen bonds. Spectral properties and structure of supramolecular complexes of bis-aza-18-crown-6-containing dienones with alkanediammonium salts

Dienones (ketocyanine dyes) containing two aza-18-crown-6 ether residues were synthesized. The complex formation of these dyes with the EtNH3+ and +H3N(CH2)nNH3+ ions (n = 2–10, 12) in MeCN was studied by electronic and 1H NMR spectroscopy, including spectrophotometric and 1H NMR titration. It was found that homoditopic bis-azacrown dienones and alkanediammonium ions with a short polymethylene chain form 1:1, 2:2, and 1:2 complexes, whereas alkanediammonium ions with a long polymethylene chain form only pseudocyclic 1:1 complexes. The stability constants of the resulting complexes were determined (logK1:1 varies in the range from 2.74 to 5.62 [M–1], logK2:2 = 2.1 [M–1], and logK1:2 varies in the range from 2.03 to 2.96 [M–1]). The most stable complexes are formed by diammonium ions with a long polymethylene chain owing to simultaneous binding of both NH3+ groups to the azacrown ether residues of the dye. The structure of supramolecular complexes was confirmed by quantum chemical calculations.

Toxicogenomic Assessment of Complex Chemical Signatures in Double-Crested Cormorant Embryos from Variably Contaminated Great Lakes Sites.

Using omics approaches to monitor complex environmental mixtures is challenging. Previously, we evaluated in vitro transcriptomic effects of complex organic extracts derived from avian eggs. However, there is a lack of studies using wild species that are naturally exposed to contaminant mixtures. Here, we examined polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) residues and gene expression in embryonic liver tissue of double-crested cormorants (Phalacrocorax auritus) collected from six variably contaminated colonies. Colonies near industrialized areas were distinguished from less contaminated sites based on their PCB and PBDE concentrations. The most variably expressed genes between sites were involved in pathways including, xenobiotic metabolism (e.g., Cyp1a4), lipid/bile acid homeostasis (e.g., Lbfabp), and oxidative stress (e.g., Mt4). Hierarchical clustering, based on relative gene expression, revealed a grouping pattern similar to chemical residue concentrations. Further, partial least squares regression analysis was used to estimate chemical concentrations from transcriptomics data. PCB 155 and BDE 47 showed the highest slopes (0.77 and 0.69, respectively) fitted by linear regression of measured and estimated chemical concentrations. The application of transcriptomics to a wild avian species, naturally exposed to complex chemical mixtures and other stressors, represents a promising means to distinguish and prioritize variably contaminated sites.

Supramolecular tuning of energy transfer efficiency and direction in a bis(styryl) dye–crown ether conjugate

The control of the energy transfer (FRET) in a novel bischromophoric styryl(pyridinium) dye bearing two different crown ether residues is presented. Complexation of the dye with metal cations allows to tune the FRET efficiency without changing the transfer direction or to switch the FRET off, whereas protonation launches the FRET process in the opposite direction relative to the molecular structure.

Brassinosteroid-induced accumulation of complex oxylipins in flax leaves

The effect of the steroid plant hormone 24-epibrassinolide on the content and composition of complex oxylipins in plants was studied for the first time, using flax as a model plant. In plants treated with the plant hormone, as well as in plants inoculated with Pectobacterium atrosepticum, the content of linolipins (galactolipids containing divinyl ether residues) increased. Hormonal pretreatment of the plants with subsequent infection resulted in a more significant accumulation of linolipins B (21-fold) and A (2.8-fold) as compared to the untreated (control) plants. The data suggest that brassinosteroids are involved in the regulation of the formation of complex oxylipins in pathogenesis of plants.

Regio- and stereoselective [2+2] photocycloaddition in Ba2+ templated supramolecular dimers of styryl-derivatized aza-heterocycles

The regio- and stereoselective [2+2] photocycloaddition of 15-crown-5-containing styrylheterocycles resulting in formation of only one cyclobutane isomer out of eleven possible is described. It was shown that the cycloaddition takes place solely in the case of the supramolecular preorganization of the reactive molecules provided by both π–π stacking interaction of the heterocyclic fragments and sandwich-type coordination of the crown ether residues by the barium cation. The results point out the importance of the supramolecular approach for the synthesis of cyclobutane derivatives with desired structure and conformation.

Dissipation behavior of octachlorodipropyl ether residues during tea planting and brewing process.

The dissipation behavior of octachlorodipropyl ether (OCDPE) residues in fresh tea shoots and in tea prepared under field conditions was investigated, and the transfer of residues from brewed tea to tea infusion was determined. OCDPE levels in tea shoots, prepared tea, tea infusion, and spent tea leaves were determined using a sensitive and simple method. The dissipation of OCDPE is fairly slow in tea shoots and prepared tea, with half-life values of 5.10 and 5.46 days, respectively. The degradation rates of OCDPE residues in tea processing were 23.9–43.1 %. The terminal residues of OCDPE in tea shoots and prepared tea samples after 20 and 30 days of OCDPE application were higher than 0.01 mg/kg. However, OCDPE’s transfer rates from brewed tea to tea infusion were only 6.0–14.8 %. Further studies on risk assessment of OCDPE residue in tea on the basis of the relationship of OCDPE in prepared tea and infusion are warranted.

Unexpected Metabolic Versatility in a Combined Fungal Fomannoxin/Vibralactone Biosynthesis.

The secondary metabolome of an undescribed stereaceous basidiomycete (BY1) was investigated for bioactive compounds. Along with a known fomannoxin derivative and two known vibralactones, we here describe three new compounds of these natural product families, whose structures were elucidated using 1D and 2D NMR spectroscopy and high-resolution mass spectrometry. The new compound vibralactone S (4) shows a 3,6-substituted oxepin-2(7H)-one ring system, which is unprecedented for the vibralactone/fomannoxin class of compounds. Stable isotope labeling established a biosynthetic route that is dissimilar to the two published cascades of oxepinone formation. Another new compound, the antifungal methyl seco-fomannoxinate (6), features a 2-methylprop-1-enyl ether moiety, which is only rarely observed with natural products. The structure of 6 was confirmed by total synthesis. (13)C-labeling experiments revealed that the unusual 2-methylprop-1-enyl ether residue derives from an isoprene unit. The diversity of BY1's combined fomannoxin/vibralactone metabolism is remarkable in that these compound families, although biosynthetically related, usually occur in different organisms.

Flavonoids and Gastroprotective Effect of Matricaria chamomilla against Indomethacin-Induced Ulcer in Rats

The antiulcer effect of Matricaria chamomilla flower head extracts were investigated on indomethacin-induced ulcer models in rats. All extracts exhibited antiulcer effect; the highest percent of inhibition was shown by the ethyl acetate and chloroform fractions (84, 80%) respectively, followed by petroleum ether and aqueous ethanol residue (57, 50%), respectively, while the total alcoholic extract showed 62%. Phytochemical investigation of the ethyl acetate fraction allowed isolation and identification of apigenin-7-methoxy -8-O-arabinopyranoside, apigenin -7-O-β-glucoside - 6″ acetate, apigenin-7-O-galactoside - 6″ acetate, and apigenin -7-O-β-glucoside, by NMR, mass analysis, and acid hydrolysis.

Metabolic incorporation of unsaturated fatty acids into boar spermatozoa lipids and de novo formation of diacylglycerols

Lipids play an important role in the maturation, viability and function of sperm cells. In this study, we examined the neutral and polar lipid composition of boar spermatozoa by thin-layer chromatography/mass spectrometry. Main representatives of the neutral lipid classes were diacylglycerols containing saturated (myristoyl, palmitoyl and stearoyl) fatty acyl residues. Glycerophosphatidylcholine and glycerophosphatidylethanolamine with alk(en)yl ether residues in the sn-1 position and unsaturated long chained fatty acyl residues in sn-2 position were identified as the most prominent polar lipids. The only glycoglycerolipid was sulfogalactosylglycerolipid carrying 16:0-alkyl- and 16:0-acyl chains. Using stable isotope-labelling, the metabolic incorporation of exogenously supplied fatty acids was analysed. Boar spermatozoa incorporated hexadecenoic (16:1), octadecenoic (18:1), octadecadienoic (18:2) and octadecatrienoic (18:3) acids primarily in the diacylglycerols and glycerophosphatidylcholines. In contrast, incorporation of eicosapentaenoic acid (20:5) was not detected. The analysis of molecular species composition subsequent to the incorporation of exogenous [14C]-octadecadienoic acid suggests two pathways for incorporation of exogenous fatty acids into glycerophosphatidylcholine: (1) de novo synthesis of glycerophosphatidylcholine via the CDP-choline pathway and (2) reacylation of lysophosphatidylcholine via an acyltransferase.

Determination of bisphenol diglycidyl ether residues in canned foodstuffs by high performance liquid chromatography-tandem mass spectrometry

An accurate quantitative determination and confirmative method for bisphenol diglycidyl ether residues, bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), bisphenol A (2,3-dihydroxypropyl) glycidyl ether (BADGE H2O), bisphenol A bis (2,3-dihydroxypropyl) ether (BADGE x 2H2O), bisphenol A (3-chloro-2-hydroxy propyl) (2,3-dihydroxypropyl) ether (BADGE x H2O x HCl), bisphenol A (3-chloro-2-hydroxypropyl) glycidyl ether (BADGE x HCl), bisphenol A bis(3-chloro-2-hydroxypropyl) ether (BADGE x 2HCl), bisphenol F bis (2, 3-dihydroxypropyl) ether (BFDGE x 2H2O), bisphenol F bis (3-chloro-2-hydroxypropyl) ether (BFDGE x 2HCl) in canned foodstuffs by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) has been established. The sample was extracted with tert-butylmethyl ether and the extract was cleaned-up and concentrated on a Waters Oasis HLB column. The target compounds were analyzed by HPLC-MS/MS on a C18 column by the gradient elution with methanol and 5 mmol/L ammonium acetate containing 0.1% formic acid in a multiple reaction monitoring (MRM) scan mode. External matrix standard solutions were used for the quantitative determination and the calibration curves showed good linearity in the concentration range of 10.0 -2 000.0 microg/L for the nine target compounds. The limits of quantification of the nine compounds were 10.0 microg/kg (S/N > or = 10). The average recoveries of the nine compounds ranged from 79.6% to 100.9% at the spiked levels of 10.0, 100.0, 1 000.0 microg/kg with the relative standard deviations (RSDs) of 6.3%-12.1%. The method is sensitive, accurate, and suitable for the rapid determination of bisphenol diglycidyl ether residues in canned foodstuffs.

P-tert-butylcalix[4]arenes containing azacrown ether substituents at the lower rim as potential polytopic receptors

A series of disubstituted p-tert-butylcalix[4]arenes with N-methoxycarbonylmonoazacrown ether and N-ethoxymonoazacrown ether residues at the lower rim has been prepared via the reaction of di(carboxymethoxy)-p-tert-butylcalix[4]arene with azacrown ethers and subsequent reduction of the resulting amide derivatives. Using UV titration and 1H NMR spectroscopy we have demonstrated the ability of the calixarene with two N-carbonylmonoaza-18-crown-6-ether substituents to form the 1:3 complexes with K+ and Na+ and the 1:2 complexes with Cs+, Sr2+, Cu2+, and Zn2+. The calixarene with two fragments of N-ethoxymonoazo-18-crown ether has formed binuclear complexes with alkali metals cations and mononuclear complexes with transition metals cations.

New trends in the kitchen: Propellants assessment of edible food aerosol sprays used on food

New products available for food creations include a wide variety of “supposed” food grade aerosol sprays. However, the gas propellants used cannot be considered as safe. The different legislations available did not rule any maximum residue limits, even though these compounds have some limits when used for other food purposes. This study shows a preliminary monitoring of propane, butane and dimethyl ether residues, in cakes and chocolate after spraying, when these gases are used as propellants in food aerosol sprays. Release kinetics of propane, butane and dimethyl ether were measured over one day with sprayed food, left at room temperature or in the fridge after spraying. The alkanes and dimethyl ether analyses were performed by headspace-gas chromatography–mass spectrometry/thermal conductivity detection, using monodeuterated propane and butane generated in situ as internal standards. According to the obtained results and regardingthe extrapolations of the maximum residue limits existing for these substances, different delays should be respected according to the storage conditions and the gas propellant to consume safely the sprayed food.

Effect of Cross-Linking on the Molecular Motions and Nanodomains Segregation in Polymethacrylates Containing Aliphatic Alcohol Ether Residues

The dielectric relaxation spectra of poly(2-ethoxyethyl methacrylate) in the frequency domain exhibits above Tg and at high frequencies a well-developed secondary γ relaxation. This process is followed in decreasing order of frequency for a relatively weak β relaxation and an ostensible glass–rubber relaxation which at high temperatures and low frequencies is dominated by electrode–polymer interfacial processes. By slightly cross-linking the polymer using 2.5% (mol) of 2-ethoxyethyldimethacrylate as cross-linking agent, the β relaxation disappears, the γ relaxation remaining. The activation energy of the γ relaxation for the cross-linked and un-cross-linked polymers is ca. 30 kJ·mol–1, about 10 kJ·mol–1 below that of the β relaxation. Cross-linking shifts the location of the glass–rubber relaxation nearly 10 °C to higher temperatures, without widening the distribution of relaxation times. The X-rays pattern of the cross-linked polymer presents two peaks at q = 5.6 nm–1 and 12.76 nm–1, resembling the X-ray patterns of poly(n-alkyl methacrylate)s. The peaks in poly(n-alkyl methacrylate)s were attributed to the formation of nanodomains integrated by side chains flanked by the backbone. However, whereas this heterogeneity produces an αPE peak in poly(n-alkyl methacrylate)s with n ≥ 2, this microheterogeneity gives rise to a Maxwell–Wagner–Sillars (MWS) relaxation in the cross-linked polymer located at lower frequencies than the glass rubber relaxation. Finally the interfacial-electrode conductive processes of the cross-linked and un-cross-linked polymeric systems are studied in the light of current theories.

Highly water-soluble neutral near-infrared emissive BODIPY polymeric dyes

Three highly water-soluble near-infrared emissive polymeric BODIPY dyes (polymers A–C) were prepared by the palladium-catalyzed Suzuki polymerization of highly water-soluble 2,6-diiodo-3,5-distyryl-BODIPY dyes with 1,4-phenyldiboronic acid and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di[1-[2-(2-methoxyethoxy)ethoxy]ethyl]fluorene, respectively. Partial replacement of fluorine subunits of BODIPY cores at 4,4-positions of polymer C with ethynyl subunits resulted in a highly water-soluble BODIPY polymeric dye (polymer D). Polymers A–D show solubility of at least 20 mg mL−1 in aqueous solution. For comparison purposes, polymers E and F were prepared by palladium-catalyzed Sonogashira polymerization of highly water-soluble 2,6-diiodo-3,5-distyryl-BODIPY dye with highly water-soluble 1,4-diethynylbenzene and 2,6-diethynyl BODIPY dye bearing branched oligo(ethylene glycol)methyl ether residues, respectively. Upon comparison, polymer E shows low solubility in aqueous solution (0.1 mg mL−1), whereas polymer F is almost insoluble in aqueous solution (less than 0.05 mg mL−1), but both are soluble in organic solvents such as chloroform, DMSO and DMF (at least 10 mg mL−1).

Three Mechanisms of Asymmetric Polymerization of Phenylacetylenes Having an l-Amino Ether Residue and Two Hydroxy Groups

Three novel chiral phenylacetylenes having an octyloxyethanolamine residue derived from a l-aminoalcohol and two hydroxymethyl groups were synthesized and polymerized by two achiral catalysts ((nbd)Rh+[η6-(C6H5)B−(C6H5)3] and [Rh(nbd)Cl]2/triethylamine (TEA)) and a chiral catalytic system ([Rh(nbd)Cl]2/(S)- or (R)-phenylethylamine ((S)- or (R)-PEA)). All of the resulting polymers showed Cotton effects at wavelengths around 430 nm. This observation indicated that they had an excess of one-handed helical backbones. Positive and negative Cotton effects were observed for the polymers having an l-valinol residue produced by using (S)- and (R)-PEA as a cocatalyst, respectively, although the monomers had the same chirality. The two polymers having an l-alaninol or l-phenylalaninol residues obtained by using (S)- and (R)-PEA as a cocatalyst showed CD absorptions with identical signs. Therefore, we found that the chiral monomer having an l-valinol residue was suitable for both modes of asymmetric polymerization, t...

Synthesis and conformational analysis of a novel carbohydrate-fused bis-crown ether: crown- CyPLOS

A novel sugar-based macrocycle consisting of a phosphate-linked 12-membered disaccharide ring (cyclic phosphate-linked oligosaccharide, CyPLOS), fused to two 18-crown-6 ether residues, is here described. The synthesis of the target compound has been accomplished in 23% overall yield for 11 reaction steps, exploiting phosphoramidite chemistry for the dimerization and a classical phosphotriester methodology for the cyclization reaction. NMR-based conformational analysis studies have been carried out on the fully deprotected macrocycle, showing a characteristic arched-structure with C 2-symmetry.

Determination of oxadiazon and oxyfluorfen in thyme by gas chromatography with electron-capture detection and gas chromatography/mass spectrometry

The present paper reports on an analytical method for the routine analysis of oxadiazon (5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2(3H)-one) and oxyfluorfen (2-chloro-α,α,α-trifluoro-p-tolyl 3-ethoxy-4-nitrophenyl ether) residues in thyme (Thymus vulgaris L. and Thymus zygis subsp. gracilis). Samples were extracted by sonication with a water-acetonitrile mixture and the herbicides were partitioned into dichloromethane. Residue levels in thyme were determined by gas chromatography with electron-capture detection (ECD). Confirmation analysis of herbicides was carried out by GC/MS in the selected ion monitoring (SIM) mode. The identification of compounds was based on retention time and on comparison of the primary and secondary ions. The average recovery by the GC-ECD method obtained for these compounds varied from 89.0 to 108.5% with a relative standard deviation between 1.9 and 6.1%. The detection limit by the GC-ECD for the pesticides studied varied from 4.9 to 13.9 µg kg−1. The proposed method was applied to thyme samples grown in the Region of Murcia (Spain). The results showed that this method provided a simple, rapid and sensitive way to analyse oxadiazon and oxyfluorfen residues in thyme.