Oxybenzoic Acid Research Articles

Fluorine and chlorine substituted adamantyl-urea as molecular tools for inhibition of human soluble epoxide hydrolase with picomolar efficacy

Series of 1,3-disubstituted ureas and diadamantyl disubstituted diureas with fluorinated and chlorinated adamantane residues were shown to inhibit human soluble epoxide hydrolase (sEH) with inhibition potency ranging from 40 pM to 9.2 nM. The measured IC50 values for some molecules were below the accuracy limit of the existing in vitro assays. Such an increase in activity was achieved by minimal structural modifications to the molecules of known inhibitors, including 4-[trans-4-(1-adamantylcarbamoylamino)cyclohexyl]oxybenzoic acid. For the chlorinated homologue of the latter the sharp jump in inhibitory activity can be (according to molecular dynamics data) the result of interactions – Cl-π interaction. Considering the extremely high inhibitory activity, acceptable solubility and partial blockage of metabolically sensitive centres in their structures, some compounds are of interest for further in vivo biotesting.

Large Range Thermochromism in Liquid Crystalline Elastomers Prepared with Intra‐Mesogenic Supramolecular Bonds

AbstractLiquid crystalline elastomers (LCEs) that retain the cholesteric phase (CLCEs) are soft, polymeric materials that retain periodic structure and exhibit a selective reflection. While prior studies have examined thermochromism in CLCEs, the association of temperature change and reflection wavelength shift has been limited to 1.4 nm °C−1. Here, CLCEs with intra‐mesogenic supramolecular bonds are prepared to enhance tunability as well triple the rate (e.g., 4.8 nm °C−1). Specifically, these materials incorporate liquid crystalline monomers based on dimerized oxy‐benzoic acid (OBA) derivatives. Increasing the concentration of the OBA comonomers increases the magnitude of red‐shifting thermochromism of the selective reflection. At and above a threshold concentration, the selective reflection in the CLCEs can disappear upon heating, analogous to on‐off “switching.” Further, the introduction of the supramolecular bonds within the CLCE enable mechanical programming and enhanced one‐time tunable thermochromism via a one‐way shape memory process. Accordingly, this research could enable functional use in low temperature sensitive optical elements, fail‐safe thermal indicators for food packaging, and smart window coatings.

CATALYSIS OF TRIVALENT PHOSPHORUS COMPOUNDS OF THE REACTIONS OF SUBSTITUTED BENZOIC ACIDS WITH ANILINE

The catalytic preparation of substituted benzanilides by the reaction of substituted benzoic acids with aniline is an important model process that has been intensively deve­lo­ped recently, in the field of the «green chemistry» concept, direct catalytic amidation, and its study is an urgent scientific and practical task.
 Within the framework of solving this problem, the catalysis of the acylation of aniline by substituted benzoic acids with trivalent phosphorus compounds P(III) was studied. It was established that P(III) in the amount of only 2% mol. from substituted benzoic acid effectively catalyze this reaction, which proceeds in boiling low-polar solvents with intensive water distillation in an air atmosphere, which leads to obtaining anilides of substituted benzoic acids with a yield close to quantitative. The new catalysts, phosphorus trichloride and tribromide, phosphorous acid, successfully complement the catalytic system tetrabutoxytitanate/polybutoxytitanate, previously used for these purposes, allowing to obtain anilides of amino­benzoic acids with greater selectivity, as well as anilides of oxybenzoic acids.
 The study of the kinetic regularities of the reaction catalyzed by phosphorus trichloride showed a weak effect of substituents: |ρ| ≤ 0.61. Hammett dependences are represented by curves with a maximum, straight line segments are characteristic only for certain groups of substituents, both for meta- and para-substituted and for orthosubstituted benzoic acids.
 One of the possible mechanisms of acylation is the formation in situ in the first mi­nutes of the reaction of aniline phosphite, which can act as an oxygen-nucleophilic catalyst, and, upon interaction with substituted benzoic acid, forms the corresponding benzoyl phosphite, which is then attacked by a free aniline molecule to obtain substituted benzanilide.
 The ortho effect for P(III) catalysis is absent or very weak, in the case of aminobenzoic acids. At the same time, anthranilic acid can form a phosphite with phosphorous acid, which directly participates in catalysis.

Biologically active agents as part of extracts of grape leaves and vine and method of their extraction

The paper experimentally assesses the characteristics of grape raw materials (vines, leaves) in terms of quantitative and qualitative composition of polyphenols - the main functional biologically active ingredients of grape processing products. For obtaining alcoholic extracts, vines and leaves of grape were pre-dispersed and extracted using the ethanol. The extraction was carried out at room temperature for several months until an equilibrium concentration of polyphenols was obtained. The extracts were separated by leaking off on a sieve. The qualitative and quantitative composition of polyphenols in alcohol extracts was determined by the HPLC method. The analysis of the obtained data shows that a broad array of polyphenols appropriate for grape pomace, seeds and stalks (flavones, flavan-3-ols, hydroxy-cinnamic, oxybenzoic acids, stilbenes, oligomeric and polymeric procyanidins) is present in vine and leaves.

Concentrates of polyphenols from grape raw materials and their functional properties

The work presents the possibility of obtaining polyphenol concentrates from raw materials (pomace, seeds, cane, vines, leaves) of Crimean grapes of white varieties Aligote, Rhine Riesling, Rkatsiteli and grapes of red varieties Muscat Hamburg, Cabernet-Sauvignon, by vacuum concentration of alcoholic extracts of grape raw materials. An experimental assessment on the qualitative and quantitative structure of polyphenols, the basic functional ingredients of biological activity of grapes has been given. It has been established that by concentration of phenolic substances, the concentrates are distributed in the following sequence: seeds of grapes of white and red varieties, stalks of grapes of white and red varieties, pomace of grapes of red varieties, leaves of grapes, vine of grapes, pomace of grapes of white varieties. In grape concentrates, anthocyanins, flavones, flavan-3-ols, oligomeric and polymeric procyanidins, oxycinnamic and oxybenzoic acids and stilbenoids have been identified. The maximum quantitative evaluation of stilbenoid concentration obtained in grape concentrates was up to 5.0 g/L, which is by order of magnitude greater than in red wines. The antioxidant activity indicator (AOA), estimated in vitro in grape seed concentrate, ranged from 180.0 to 250.0 g/l, which is by order of magnitude greater than in red grape wines.

Induction of Wheat Resistance against the Causative Agent of Basal Bacteriosis with Growth-Promoting Bacteria

Using a cell suspension of growth-promoting bacteria (Bacillus subtilis) in spring wheat plants of the Granny variety generates a 25% increase in the level of their resistance against the causative agent of basal bacteriosis (Pseudomonas syringae pv. atrofaciens). The study established the initiation of the synthesis of cell-wall biopolymers, in particular, cellulose, lignin, and suberin, and the accumulation of the content of oxycoric and oxybenzoic acids in plant leaves.

Phenolic complex of red wine materials from grapes growing in the Crimea

The research work presents the results of studies of the composition of anthocyanins, monomeric forms of phenolic substances, oligomeric procyanidins, polymer forms of phenolic substances in wine materials Cabernet Sauvignon, Merlot, Syrah, Petit Verdot, Sangiovese, Marcelan obtained from grapes growing in the Crimea. It was found that the main coloring material in the wine materials under study was malvidin-3-O-glycoside. The proportion of this compound ranged from 42.9% to 54.3% in the total of all anthocyanins. The highest mass concentrations of oxybenzoic and hydroxycinnamic acids are determined in the wine material Marcelan. In the Sangiovese wine material, the highest concentrations of flavan-3-ols are determined. Mass concentrations of quercetin-3-O-glucoside in the test samples were 4-17 mg/dm3; quercetin - 1-7 mg/dm3. Mass concentrations of oligomeric procyanidins were in the range of 106-240 mg/dm3 and the highest value was determined in the wine material Marcelan, the lowest Cabernet Sauvignon. Mass concentrations of polymer forms of phenolic substances amounted to 1487-2998 mg/dm3.

One-dimensional Lanthanide Coordination Polymers Based on Butylene-2,2'-bis(oxybenzoic Acid), with Dy-compound Exhibiting White Light Emission

A series of one-dimensional (1D) lanthanide coordination polymers: [Ln2(BBOA)3(H2O)]n (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), H2BBOA = butylene-2,2′-bis(oxybenzoic acid)) were synthesized under hydrothermal methods and structurally characterized by single-crystal X-ray diffraction. Compounds 1, 2, 4, 5 are isostructural belonging to the triclinic system with space group P-1. Due to the disorder, the similar structure compound 3 has a double asymmetric unit comparing to others. Luminescence analyses were performed on coordination polymers containing Sm3+, Eu3+ and Tb3+ and Dy3+, and compound 5 shows a white light emission upon excitation. Magnetic properties of complexes 3 to 5 were measured, and complexes 4 and 5 exhibit ferromagnetic behavior.

Вплив оксикоричних і оксибензойних кислот на метаболізм та регенераційні процеси в експлантатах троянди ефіроолійної у культурі in vitro

Вплив оксикоричних і оксибензойних кислот на метаболізм та регенераційні процеси в експлантатах троянди ефіроолійної у культурі in vitro

Anti-oxidant components from the aerial parts of Asterothamnus centrali-asiaticus

Two new phenolic acids 2-hydroxy-5-[(6⿲-O-(E)-caffeoyl)-β-d-glucopyranosyl]-oxybenzoic acid (1) and 2-hydroxy-5-[(3⿲-O-(E)-caffeoyl)-β-d-glucopyranosyl]-oxybenzoic acid (2) were isolated from the aerial parts of Asterothamnus centrali-asiaticus, together with five known ones (3-7). Their structures were elucidated by extensive 1D and 2D NMR studies and HRESIMS investigations. The anti-oxidant activity of the isolates was evaluated through ABTS radical cation decolorization assay. The results showed that all of them exhibited anti-oxidant activity, and compound 7 was the most active compound with an IC50 value of 7.65μg/mL.

Спектрофотометрическое определение суммы фенольных соединений в растительных объектах с использованием хлорида алюминия, 18-молибдодифосфата и реактива Фолина-Чокальтеу

It was concluded from the results of the analysis of a number of drugs on the basis of vegetable raw materials such as tablets, tinctures, syrups, medicinal plants, fruits, teas, etc., that 18-molybdodiphosphate heteropoly anion ( 18-MPA ) and Folin-Ciocalteu (FCR) reagents were suitable for the spectrophotometric determination of the total content of phenolic compounds. This conclusion was confirmed by a high degree of correlation ( R 2 > 0,95) between the results obtained by the two methods. In many cases, the absolute difference between the results of both methods was low, and that was an evidence of closeness of apparent molar absorptivity values calculated for the reactions with the above mentioned reagents. Interaction of polyphenols with 18-MPA at pH 7.4 was rapid and complete when the total content of polyphenols was determined by the presence of flavonols or cinnamic acids. Range of pH > 9.0 was optimal for the determination of less reactive compounds (polymeric polyphenols, catechins, oxybenzoic acids). The results of the polyphenols sum determination obtained with 18-MPA or FCR reagents correlated with the results obtained using the aluminium chloride method only in the case when flavons with hydroxy groups in the positions 3 and/or 5 were dominating phenol species present in the plants. Keywords: 18-molybdophosphate heteropoly complex, Folin-Ciocalteu reagent, aluminium chloride, spectrophotometric analysis, determination of phenols (Russian) DOI: http://dx.doi.org/10.15826/analitika.2015.19.4.012 T . A . Denisenko , A . B . Vishnikin , L . P . Tsiganok Oles Honchar Dnipropetrovsk National University , Dnipropetrovsk , Ukraine

Local modes of molecular mobility in comb-shaped liquid crystalline ionomers containing alkaline metal ions

Molecular mobility of the comb-shaped copolymer poly(4-[6-(acryloyloxy)hexyloxy]benzoic acid- co-butyl acrylate) and Li- and Rb-containing LC ionomers based on this polymer was studied at low temperatures by the methods of dielectric spectroscopy and thermally stimulated depolarization current. The above copolymers are shown to experience the γ 2, γ 1, and β-processes, which are related by the reorientation of the end СООН groups, by the mobility of a spacer, and by the reorientation of mesogenic fragments (dimers of oxybenzoic acids) with respect to a long axis, respectively. The formation of multiplet structures in ionomers leads to a suppression of the intensity of the β-process that relates with a partial breakdown of hydrogen-bonded dimmers and with a decrease of their molecular mobility.

New and Simple Synthetic Method for Carboxylic Acid Functionalized Poly(ethylene glycol)

Alkylation of methyl 4-hydroxybenzoate with α-methoxy-ω-methanesulfonylpoly(ethylene glycol) (M = 5 000) and α,ω-bismethanesulfonylpoly(ethylene glycol) (M = 10 000) has been used to prepare 4-poly(ethylene glycol)oxybenzoic acids. Reactions of chlorides of these acids with 2-amino-2-methylpropanenitrile or 2-amino-2,3-dimethylbutanenitrile were used to prepare the corresponding acylaminonitriles, which were subsequently cyclized and hydrolyzed to give the following acylamino acids: 2-{4-[α-methoxy­poly(ethylene glycol)]oxybenzoylamino}-2,3-dimethyl­butyric acid and 2-(4-{α-[4-(1-carbonyl-1-methylethylcarb­amoyl)phenoxy]poly(ethylene glycol)-ω-yloxy}benzoylamino)-2-methylpropionic acid.

Fan-shaped, toric and spherulitic textures of mesomorphic oxadiazoles

When a family of non-symmetrical heterocycled compounds is investigated, a variety of mesophases can be observed with rather different features. Here we report the behaviour of seven different members among a family of such materials, which consists of mesomorphic oxadiazole compounds. In two of these compounds, the optical microscope investigation shows very interesting behaviours. In their smectic phases, fan-shaped and toric textures, sometimes with periodic instability, are observed. Moreover, the nematic phase displays a texture transition. Texture transitions have been previously observed only inside the nematic phase of some compounds belonging to the families of the oxybenzoic and cyclohexane acids. In these two oxadiazole compounds we can observe a nematic phase with a spherulitic texture, heating the samples from the smectic phase. This nematic texture disappears as the sample is further heated, changing into a smooth texture.

DISTRIBUTION OF (7α)-21-[4-[(DIETHYLAMINO) METHYL]-2-METHOXYPHENOXY]-7-METHYL-19-NORPREGNA-1,3,5(10)-TRIEN-3-OL-20-[14C]2-HYDROXY-1,2,3-PROPANETRICARBOXYLATE ([14C]TAS-108) AND ITS METABOLITES AFTER SINGLE ORAL ADMINISTRATION TO RATS BEARING 7,12-DIMETHYLBENZ(α)ANTHRACENE-INDUCED MAMMARY TUMOR

(7Alpha)-21-[4-[(diethylamino)methyl]-2-methoxyphenoxy]-7-methyl-19-norpregna-1,3,5(10)-trien-3-ol 2-hydroxy-1,2,3-propanetricarboxylate (TAS-108) is a novel steroidal antiestrogen, modulating the differential recruitment of transcriptional cofactors by liganded estrogen receptors and representing a promising agent for the treatment of breast cancer. To understand better the relationships between the drug exposure and the efficacy or toxicity of TAS-108, we investigated the metabolism and distribution of TAS-108 after oral administration of [14C]TAS-108 to rats bearing a 7,12-dimethylbenz(alpha)anthracene-induced mammary carcinoma. The metabolites (7alpha)-21-[4-[(ethylamino)methyl]-2-methoxyphenoxy]-7-methyl-19-norpregna-1,3,5(10)-trien-3-ol (deEt-TAS-108), (7alpha)-21-[4-[(diethylamino)methyl]-2-methoxyphenoxy]-7-methyl-19-norpregna-1,3,5(10)-trien-3-ol-N-oxide (TAS-108-N-oxide), and 3-methoxy-4-[(7alpha)-7-methyl-19-norpregna-1,3,5(10)-trien-3-ol-21-yl]oxybenzoic acid (TAS-108-COOH) were identified as the major metabolites in the plasma, and in addition, (7alpha)-21-[4-[(ethylamino)methyl]-2-methoxyphenoxy]-3-methoxy-7-methyl-19-norpregna-1,3,5(10)-triene (O-Me-deEt-TAS-108) was identified as a novel metabolite in this study. The time-concentration profiles of TAS-108 and its metabolites in the plasma were compared with those in the tumor and uterus of the rats. Radioactivity was found at a high level in various organs including lung, liver, spleen, ovary, and many glands at 12 h and was relatively higher in tumor tissue than in plasma. On the other hand, the levels of radioactivity in the brain and eyeball were very low or not detectable. TAS-108, deEt-TAS-108, and O-Me-deEt-TAS-108 were extensively distributed in the rat tissues and the tumor, with corresponding tissue/plasma ratios for Cmax and area under the curve in the range of 7 to 100. In contrast, TAS-108-COOH and TAS-108-N-oxide were hardly distributed to the tissues and thus may not contribute to the efficacy or toxicity of TAS-108. Thus, TAS-108, deEt-TAS-108, and O-Me-deEt-TAS-108, being distributed highly in tumor tissue, may be more important for the efficacy and toxicity of TAS-108 in vivo than TAS-108-COOH and TAS-108-N-oxide.

Influence of short distance sequence regularity on preparation of poly( p-oxybenzoyl- co- p-mercaptobenzoyl) whisker

Preparation of the poly( p-oxybenzoyl- co- p-mercaptobenzoyl) whiskers was examined by means of the crystallization of oligomers during solution polymerization. Polymerizations were carried out in liquid paraffin at the concentration of 1.0% and 300 °C for 6 h. Copolymerization of 4-acetoxybenzoic acid and S-acetyl-4-mercaptobenzoic acid did not yield the whiskers. This was attributed to tendency that the copolymerization reduced the crystallizability of oligomers and induced the liquid–liquid phase separation of oligomers due to the lower freezing point. In order to induce short distance sequence regularity into oligomers, copolymerizations of two among four monomers were conducted, which were 4-(4-acetoxybenzoyl)oxybenzoic acid, S-(4-acetoxybenzoyl)-4-mercaptobenzoic acid, 4-( S-acetyl-4-mercaptobenzoyl)oxybenzoic acid and S-( S-acetyl-4-mercaptobenzoyl)-4-mercaptobenzoic acid. The copolymerizations of two of these monomers yielded the whiskers but for that of 4-(4-acetoxybenzoyl)oxybenzoic acid and S-( S-acetyl-4-mercaptobenzoyl)-4-mercaptobenzoic acid. The short distance sequence regularity of oligomers brought about the crystallization of oligomers, leading to the formation of whiskers.

Self-Assembling Polycondensation for Preparation of Poly(p-oxybenzoyl-alt-p-mercaptobenzoyl) Whisker

Self-assembling polycondensation was examined to prepare the whisker of poly(p-oxybenzoyl-alt-p-mercaptobenzoyl). Polymerizations were carried out in liquid paraffin (LPF) and aromatic solvents such as Therm S 800 and 1000 at 300 °C for 6 h. Polymerization concentration was 1.0 wt/vol %. The whisker was not obtained by the random copolymerization of p-acetoxybenzoic acid and S-acetyl-4-mercaptobenzoic acid at the molar ratio of 0.5 in feed. However, the whiskers were successfully prepared by the polymerization of S-(4-acetoxybenzoyl)-4-mercaptobenzoic acid (OS) and 4-(S-acetyl-4-mercaptobenzoyl)oxybenzoic acid (SO). The whisker prepared from OS (POS) in LPF was 18 μm in average length and 0.4 μm in average width, and that from SO (PSO) was slightly longer than POS. The whiskers prepared in aromatic solvents were much longer than those in LPF, for which the length was 36−49 μm. These whiskers consist of the alternating polymer chains, and the polymer chains align along the long axis of the whisker. The sequence regularity enhanced the crystallizability of the oligomers, and this led to the formation of whiskers. The oligomer formation rate was much higher than that of transesterfication reaction rate, and this large difference in these two rates made the oligomer precipitate with maintaining the alternating sequence. Further polymerization occurred in the crystals, and the whiskers having the alternating sequence were finally completed. The difference in the two rates increased with the decrease of the miscibility between the oligomer and the solvent, and therefore, OS and LPF were more advantageous to maintain the alternating sequence.

Synthesis and characterization of aromatic poly(ether ketone)s containing cyclotriphosphazene units

Bis(4-oxybenzoic acid) tetrakis(phenoxy) cyclotriphosphazene (IUPAC name: 4-[4-(carboxyphenoxy)-2,4,6,6-tetraphenoxy-1,3,5,2λ5,4λ5,6λ5-triazatriphosphinin-2-yl]oxy-benzoic acid) was synthesized and direct polycondensed with diphenylether or 1,4-diphenoxybenzene in Eaton's reagent at the temperature range of 80–120°C for 3 hours to give aromatic poly(ether ketone)s. Polycondensations at 120°C gave polymer of high molecular weight. Incorporation of cyclotriphosphazene groups in the aromatic poly(ether ketone) backbone greatly enhanced the solubility of these polymers in common organic polar solvents. Thermal stabilities by TGA for two polymer samples of polymer series ranged from 390 to 354°C in nitrogen at 10% weight loss and glass transition temperatures (Tg) ranged from 81.4 to 89.6°C by DSC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1227–1232, 1998

Somatic Embryogenesis and Plant Regeneration in Suspension Cultures of Dessert (AA and AAA) and Cooking (ABB) Bananas (Musa spp.)

Proembryogenic calli were initiated from basal leaf sheaths and rhizome tissue on modified Schenk and Hildebrandt (SH) medium with 30 μM 3,6–dichloro–2–meth–oxybenzoic acid (Dicamba). Cell suspensions were maintained in half–strength Murashige and Skoog (MS) medium supplemented with 20 μM Dicamba. The development of somatic embryos was promoted in cell suspensions 3–4 weeks after subculture in liquid modified MS medium with 5 μM zeatin. Characteristic stages of embryonic development were recapitulated and histological examination confirmed bipolar organization of somatic embryos. Conversion into plantlets took place in double layer media system composed of solid half strength MS medium with 5 μM zeatin and 1 g/l charcoal and liquid, hormone–free, half strength MS medium. In four Musa genotypes several hundred plantlets were regenerated and transferred into soil where they continued to grow. Somatic embryogenesis represents a significant step in developing a new breeding strategy for apomictic banana and plantain species.

Structural characteristics of highly oriented fibres of polyethyleneterephthalate-oxybenzoic acid copolymers, prepared from a liquid-crystalline melt

Highly oriented fibres of copolymers of polyethyleneterephthalate with oxybenzoic acid, containing 60 to 80% of the latter, were studied by X-ray methods. The fibres were prepared by extrusion from a liquid-crystalline melt at various temperatures. It was shown that the partially crystalline structure of the studied fibres is characterized by longitudinal dimensions of crystalline domains on the order of several hundred Å, while the lateral packing of macromolecules only exhibits short distance order extending to 10–30 Å. An increased content of oxybenzoic acid units leads to improved ordering in the system. It was shown that the degree of orientational order in the fibres is very high, and the macromolecular orientation function attains values of 0·93–0·99.