Methanolic Sodium Research Articles

Synthesis and Biological Evaluation of Chalconyl Incorporated Schiff’s Bases of Sulphonamides

A series of of Chalconyl Incorporated Schiff’s Bases of Sulphonamides was synthesized by reacting substituted chalcone derivatives with Sulphacetamide sodium in methanol. All the title compounds synthesized (2a-2d) were tested for antibacterial and antifungal activity using E. coli, P. aeruginosa, S. aureus, S. pyogenus and C. albicans, A. niger and A. clavatus respectively as microbial strains and Sulphacetamide sodium as standard. The compound 2d showed significant antibacterial activity and 2a showed moderate antifungal activity as compared with Sulphacetamide Sodium.

2-Hydroxyethoxy-closo-undecahydrododecaborate(12)([B12H11CH2CH2OH]2−) as a new prospective reagent for the preparation of closo-dodecaborate building blocks and thymidine and 2-deoxyuridine conjugates linked via short spacer

Reaction of dioxonium derivative of closo-dodecaborate ([B12H11O+(CH2)4O]−) with an access of NaCN in boiling EtOH led to [B12H11OCH2CH2OH]2− with an excellent yield as a result of ring cleavage followed by elimination of acrylonitrile. The same entry in aprotic DMFA afforded regular ring cleavage product [B12H11OCH2CH2OCH2CH2CN]2. Subsequent work up of this nitrile with sodium methanolate in MeOH led to the alcohol ([B12H11OCH2CH2OH]2−) as well. The above alcohol was converted into new functionalized derivatives [B12H11OCH2CH2OMs]2− and [B12H11OCH2CH2N3]2− respectively using straightforward organic reactions. These new building blocks were employed for the preparation of novel closo-dodecaborate pyrimidine nucleoside conjugates.

Affinity capillary electrophoresis and quantum mechanical calculations applied to investigation of [Gly6 ]-antamanide binding with sodium and potassium ions.

ACE in a free solution and quantum mechanical density functional theory have been applied to the investigation of interactions of glycine-6-antamanide ([Gly6 ]AA), a synthetic derivative of cyclic decapeptide antamanide isolated from the highly poisonous mushroom Amanita phalloides, with sodium or potassium ions in methanol. First, from the dependence of effective electrophoretic mobility of [Gly6 ]AA on Na+ or K+ ions concentration in the BGE (methanolic solution of 20 mM chloroacetic acid, 10 mM Tris, pHMeOH 7.8, containing 0-50 mM NaCl or 0-40 mM KCl), the apparent binding (stability) constants of [Gly6 ]AA-Na+ and [Gly6 ]AA-K+ complexes were evaluated as 26 ± 1 and 14 ± 1L/mol, respectively. The employed ACE method included correction of the effective mobilities measured at ambient temperature and at variable ionic strength of the BGEs to the mobilities related to the reference temperature 25°C and to the constant ionic strength 10 mM. Second, the interaction energies of the [Gly6 ]AA-Na+ and [Gly6 ]AA-K+ complexes (-466.3 and -345.2 kJ/mol, respectively) and the structural details of these complexes, such as position of the Na+ and K+ ions in the cavity of the [Gly6 ]AA molecule and the interatomic distances within these complexes, were determined by the density functional theory calculations.

Comparative Antimicrobial Efficacy of Eucalyptus Galbie and Myrtus Communis L. Extracts, Chlorhexidine and Sodium Hypochlorite against Enterococcus Faecalis.

Introduction:The aim of this study was to evaluate the antimicrobial effect of Eucalyptus galbie and Myrtus communis L. methanolic extracts, chlorhexidine (CHX) and sodium hypochlorite (NaOCl) on Enterococcus faecalis (E. faecalis) as the predominant species isolated from infected root canals. Methods and Materials:One hundred twenty mandibular premolars were randomly divided into 8 groups: Eucalyptus galbie (E. galbie) 12.5 mg/mL, Myrtus communis L. (M. communis L.) 6.25 mg/mL, 0.2% CHX, %2 CHX, 2.5% NaOCl, 5.25% NaOCl, positive and negative control group. Sampling was performed using paper points (from the root canal space lumen) and Gates-Glidden drills (from the dentinal tubules); then colony forming units (CFU) were counted and analyzed using the Kruskal-Wallis test, followed by Mann Whitney U test. The level of significance was set at 0.05. Results:All irrigants reduced more than 99% of bacteria in root canal. In the presence of M. communis L. and E. galbie, the bacterial count in dentin were significantly more than CHX and NaOCl groups (P<0.05) except 0.2% CHX in 200 µm and 400 µm depths (P>0.05).Conclusion:Although 5.25% NaOCl was the most effective irrigant, all agents exerted acceptable antimicrobial activity against E. faecalis.

Synthesis of Some New Nucleoside Analogues Containing Seven Membered Ring and Studying Their Biological Activity

In this work, a series of new Nucleoside analogues (D-galactopyranose linked to oxepanebenzimidazole moiety) was synthesized via multisteps synthesis. The first step involved preparation of two benzimidazoles 2-styrylbenzimidazole and 2-(phenyl ethynyl) benzimidazole via reaction of phenylenediamine with cinnamic acid or ?-phenyl propiolic acid. Electrophilic addition of the prepared benzimidazoles by three anhydrides in the second step afforded (4-6) and (14-16) which in turn were treated with 1,2,3,4-di-O-isopropylidene galactopyranose in the third step to afford a series of the desirable protected nucleoside analogues (7-9) ,(17-19)which after hydrolysis in methanolic sodium methoxidein the fourth step afforded the free nucleoside analogues (10-12) and (20-22) .The synthesized compounds were identified by FT-IR and some of them by 1H-NMR and13C-NMR. The synthesized oxepane nucleoside analogues were screened for their antibacterial activity against three types of bacteria including Staphylococcusaureus ,Bacillus(gram positive) andE.coli (gram negative) bacteria repectively.

Steroidal Ammonium Compounds as New Neuromuscular Blocking Agents.

Neuromuscular blocking agents are widely used as an anesthesia auxiliary in surgery, which induce relaxation of skeletal muscles by blocking signal transmission at the neuromuscular junction. Many neuromuscular blocking agents s were developed over the past decades, but none of them fully meets the needs of the clinic by various reasons. In this study, a series of quaternary ammonium steroidal neuromuscular blocking agents were synthesized and evaluated on isolated mouse phrenic nerve-hemidiaphragms for their bioactivities. The initial separation of mono- and bis-quaternary ammonium compounds turned out to be very challenging on regular silica gel chromatography. Therefore, a facile purification method, in which the silica gel was pretreated with methanolic sodium bromide solution, was finally achieved. Compounds 3g (0.36 μm) and 4g (0.37 μm) exhibited excellent neuromuscular blocking activities, which were about sixfold to sevenfold higher in potency than that of rocuronium (2.50 μm). In addition, other bis-quaternized compounds also showed good potencies close to that of rocuronium. Furthermore, the preliminary structure-activity relationship of this series was also elucidated. Benzyl group was found to be a promising quaternary group in this series.

Synthesis of Some New Nucleoside Analogues Containing Seven Membered Ring and Studying Their Biological Activity

In this work, a series of new Nucleoside analogues (D-galactopyranose linked to oxepanebenzimidazole moiety) was synthesized via multisteps synthesis. The first step involved preparation of two benzimidazoles 2-styrylbenzimidazole and 2-(phenyl ethynyl) benzimidazole via reaction of phenylenediamine with cinnamic acid or ?-phenyl propiolic acid. Electrophilic addition of the prepared benzimidazoles by three anhydrides in the second step afforded (4-6) and (14-16) which in turn were treated with 1,2,3,4-di-O-isopropylidene galactopyranose in the third step to afford a series of the desirable protected nucleoside analogues (7-9) ,(17-19)which after hydrolysis in methanolic sodium methoxidein the fourth step afforded the free nucleoside analogues (10-12) and (20-22) .The synthesized compounds were identified by FT-IR and some of them by 1H-NMR and13C-NMR. The synthesized oxepane nucleoside analogues were screened for their antibacterial activity against three types of bacteria including Staphylococcusaureus ,Bacillus(gram positive) andE.coli (gram negative) bacteria repectively.

Determination of Labeled Fatty Acids Content in Milk Products, Infant Formula, and Adult/Pediatric Nutritional Formula by Capillary Gas Chromatography: Collaborative Study, Final Action 2012.13.

A collaborative study was conducted on AOAC First Action Method 2012.13 "Determination of Labeled Fatty Acids Content in Milk Products and Infant Formula by Capillary Gas Chromatography," which is based on an initial International Organization for Standardization (ISO)-International Dairy Federation (IDF) New Work Item that has been moved forward to ISO 16958:2015|IDF 231:2015 in November 2015. It was decided to merge the two activities after the agreement signed between ISO and AOAC in June 2012 to develop common standards and to avoid duplicate work. The collaborative study was performed after having provided highly satisfactory single-laboratory validation results [Golay, P.A., & Dong, Y. (2015) J. AOAC Int. 98, 1679-1696] that exceeded the performance criteria defined in AOAC Standard Method Performance Requirement (SMPR(®)) 2012.011 (September 29, 2012) on 12 products selected by the AOAC Stakeholder Panel on Infant Formula (SPIFAN). After a qualification period of 1 month, 18 laboratories participated in the fatty acids analysis of 12 different samples in duplicate. Six samples were selected to meet AOAC SPIFAN requirements (i.e., infant formula and adult nutritionals in powder and liquid formats), and the other Six samples were selected to meet ISO-IDF requirements (i.e., dairy products such as milk powder, liquid milk, cream, butter, infant formula with milk, and cheese). The fatty acids were analyzed directly in all samples without preliminary fat extraction, except in one sample (cheese). Powdered samples were analyzed after dissolution (i.e., reconstitution) in water, whereas liquid samples (or extracted fat) were analyzed directly. After addition of the internal standards solution [C11:0 fatty acid methyl ester (FAME) and C13:0 triacylglycerols (TAG)] to the samples, fatty acids attached to lipids were transformed into FAMEs by direct transesterification using methanolic sodium methoxide. FAMEs were separated using highly polar capillary GLC and were identified by comparison with the retention times of pure analytical standards. Quantification of fatty acids was done relative to C11:0 FAME as internal standard and to instrument response factors (determined separately using calibration standards mixture). The performance of the method (i.e., transesterification) was monitored in all samples using the second internal standard, C13:0 TAG. RSDR values were summarized separately for labeled fatty acids in SPIFAN materials and ISO-IDF materials due to different expression of results. This method was applied to representative dairy, infant formula, and adult/pediatric nutritional products and demonstrated global acceptable reproducibility precision for all fatty acids analyzed (i.e., 46 individuals and/or groups) for these categories of products.

Interesterification, chemical or enzymatic catalysis

The interesterification process is one of the oil modification processes the refiner can use to alter the physical properties of oils and fats, The reaction requires a catalyst to proceed. This can be a base or a lipase enzyme. In the currently accepted mechanism of the base‐catalysed interesterification reaction, two anionic intermediates are involved: the enolate anion and the glycerolate anion. The presence of the enolate anion explains why an equivalent amount of FAMEs are formed when sodium methanolate is added to oil and why FFAs are formed when the catalysts is inactivated with water. Based on this insight, process development can aim at avoiding these by‐products and thereby increase the cost advantage of the chemical process over the enzymatic process even further. The chemical process is also more flexible than the solely continuous enzymatic process, which latter requires extensive purification of the oil to be interesterified.

Design and synthesis of 3-(4-aminophenyl)-5-(4-methoxyphenyl)-4,5-dihydro-1H-pyrazole-1-carboxamide/carbothioamide analogues as antitubercular agents

Emergence of multi-drug resistant tuberculosis (MDR-TB) and HIV-TB co-infections potentiate the development of newer antitubercular agents to combat against tuberculosis, a dreadful disease. In the present investigation a series of pyrazoline analogues were designed and synthesized based on the structure of known antitubercular agent thiacetazone, in hope of obtaining new and safe antitubercular agents. The target molecules were synthesized in two steps, starting with the condensation of 4-aminoacetophenone and p-anisidine in methanolic sodium hydroxide solution followed by the cyclization of intermediate chalcones with appropriate semicarbazide/thiosemicarbazide in glacial acetic acid. All the synthesized compounds were characterized by 1H NMR, IR and mass spectral data and the purity of the compounds was checked by elemental analysis. Their antimycobacterial activity was evaluated by two folds serial dilution method. 3-(4-Aminophenyl)-N-(4-chlorophenyl)-4,5-dihydro-5-(4-methoxyphenyl)pyrazole-1-carboxamide (4i) showed maximum activity against Mycobacterium tuberculosis H37Rv with minimum inhibitory concentration (MIC) of 7.41 μM.

A novel method to analyze the degree of acetylation in biopolymers

A novel approach to measure the degree of acetylation in biopolymers applying a combination of Zemplén-deacetylation by sodium methanolate and GC–MS methodology is introduced. The development focuses on very low limits of detection to cover also samples with extremely low degrees of acetylation which hitherto eluded accurate determination. Free acetic acid or inorganic acetates, often present in biopolymer samples, do not disturb the quantification. Two techniques to measure the Zemplén-released methyl acetate were comparatively assessed, direct injection of the liquid phase and a SPME-based approach, the former being more straightforward, but being inferior to the latter in sensitivity. By applying isotopically labeled methyl acetate released from 4-O-(13C2-acetyl)-vanillin as the internal standard, influences, such as varying moisture contents, are corrected, improving the overall method reliability to a large extent. The combination of Zemplén-release of acetyl groups in biopolymers as methyl acetate, in connection with its accurate quantification by SPME–GC–MS, was found to be the method of choice for routine, yet very accurate analysis of a wide range of acetylation degrees of biopolymers, showing satisfying analytical parameters along with easy handling and widest applicability. Limit of detection for acetylated cellulose samples is 0.09nmol/mg, for hemicellulose samples 0.48nmol/mg.

Determining the fatty acid composition in plasma and tissues as fatty acid methyl esters using gas chromatography – a comparison of different derivatization and extraction procedures

Analysis of the fatty acid (FA) composition in biological samples is commonly carried out using gas liquid chromatography (GC) after transesterification to volatile FA methyl esters (FAME). We compared the efficacy of six frequently used protocols for derivatization of different lipid classes as well as for plasma and tissue samples. Transesterification with trimethylsulfonium hydroxide (TMSH) led to insufficient derivatization efficacies for polyunsaturated FAs (PUFA, <50%). Derivatization in presence of potassium hydroxide (KOH) failed at derivatizing free FAs (FFAs). Boron trifluoride (BF3) 7% in hexane/MeOH (1:1) was insufficient for the transesterification of cholesterol ester (CE) as well as triacylglycerols (TGs). In contrast, methanolic hydrochloric acid (HCl) as well as a combination of BF3 with methanolic sodium hydroxide (NaOH+BF3) were suitable for the derivatization of FFAs, polar lipids, TGs, and CEs (derivatization rate >80% for all tested lipids). Regarding plasma samples, all methods led to an overall similar relative FA pattern. However, significant differences were observed, for example, for the relative amount of EPA+DHA (n3-index). Absolute FA plasma concentrations differed considerably among the methods, with low yields for KOH and BF3. We also demonstrate that lipid extraction with tert-butyl methyl ether/methanol (MTBE/MeOH) is as efficient as the classical method according to Bligh and Dyer, making it possible to replace (environmentally) toxic chloroform.We conclude that HCl-catalyzed derivatization in combination with MeOH/MTBE extraction is the most appropriate among the methods tested for the analysis of FA concentrations and FA pattern in small biological samples. A detailed protocol for the analysis of plasma and tissues is included in this article.

Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars.

Higher aminosugars are interesting targets in carbohydrate synthesis since these compounds play important roles in biological systems. However, their availability from natural sources is limited. Thus, in order to investigate their biological function, the development of facile and adaptable routes to this class of compounds is of fundamental importance. Our synthetic route towards these target molecules makes use of readily accessible pentoses and hexoses, which are subjected to indium-mediated two-carbon chain elongation. Subsequent ozonolysis and treatment with base yields α,β-unsaturated aldehydes, which are stereoselectively epoxidized using Jørgenson’s protocol. After Wittig chain elongation the obtained allylic epoxides were regio- and stereoselectively opened with trimethylsilyl azide under palladium catalysis. Finally, a suitable deprotection protocol, starting with acidic acetate cleavage and ozonolysis was established. Peracetylation of the products simplifies purification and subsequent azide reduction followed by final deacetylation using methanolic sodium methoxide furnishes the title compounds.

Orthoamide und Iminiumsalze, LXXXIII [1]. Die Synthese von starken Formylierungsmitteln im präparativen Großmaßstab: Triformamid (Triformylamin) / Orthoamides and Iminium Salts LXXXIII [1]. The Synthesis of Strong Formylating Reagents on Large Preparative Scale: Triformamide (Triformylamine)

The preparation of sodium diformamide (7) from formamide and sodium methanolate under azeotropic removal of methanol with cyclohexane, or from formamide and sodium ethanolate in ethanol, is described. Diformamide (8) can be prepared by treatment of sodium diformamide (7) with formic acid. Triformamide (triformylamine) (1) is formed in the reaction of sodium diformamide with inorganic acid halides such as SOCl2, SO2Cl2 or PCl3 in acetonitrile at low temperatures. Triformamide (1) can be prepared on a large scale by the action of methanesulfonyl chloride on finely powdered sodium diformamide (7) in acetonitrile. Tris(diformylamino)methane (4) can be formed as a side product. A procedure was developed for the large-scale preparation of N;N-diformylacetamide (6) from sodium diformamide and acetyl chloride. Triformamide (1) can be prepared from N;Ndiformylacetamide (6) and diformamide with good yields

Synthesis and Reactions of New Chiral Linear Carboxamides with an Incorporated Peptide Linkage Using Nalidixic Acid and Amino Acids as Starting Materials

4b A series of chiral linear carboxamide derivatives (2- 15) with an incorporated peptide linkage have been prepared via the coupling of 1-ethyl-1,4-dihydro-7-methyl-4-oxo-quinoline-3-carboxylic acid (nalidixic acid, 1) with appropriate amino acid methyl esters. Coupling of 1 with amino acid methyl esters gave the corresponding peptide methyl esters 2, which were hydrolyzed with methanolic sodium hydroxide to the corresponding acids 3. Hydrazinolysis of esters 2with hydrazine hydrate afforded the corresponding acid hydrazide derivatives 4. The latter compounds were coupled with appropriate aldehydes or acetophenone derivatives to afford the corresponding Schiff base derivatives 5 and 6, respectively. The hydrazide derivative was reacted with phenyl isothiocyanate or carbonyl derivatives to give the corresponding thiosemicarbazide 7 and compounds 8- 10, respectively. Also, 4b was treated with acid monoanhydrides to give the corresponding imide derivatives 11- 13. Finally, 4b was reacted with tetracarboxylic acid dianhydride derivatives to afford the corresponding diimido carboxamide derivatives 14 and 15

Green synthesis and antibacterial evaluation of some 2-pyrazoline derivatives

A Chalcone (3) was prepared by the reaction of 4-methylbenzaldehyde (1) with 4-methylacetophenone (2) in methanolic sodium hydroxide result under ultrasonic irradiation in the water bath of a ultrasonic cleaner at room temperature. Treatment of this chalcone with thiosemicarbazide / semicarbazide hydrochloride / benzhydrazide / benzenesulphonyl hydrazide / phenylhydrazine hydrochloride managed the comparing 2-pyrazoline (4-8) in great yields. All the new mixes have been described by IR, 1H-NMR, 13CNMR ghostly information. All the target mixes were assessed for their in-vitro against antifungal in examination with as reference pill. Keywords: 4-Methylbenzaldehyde, 4-Methyl Acetophenone, Ultrasonic Irradiation, Chalcone, 2-Pyrazoline, Antibacterial.

Pyrazolato-bridged arylpalladium(II) complexes, [Pd2Ar2(μ-pz/dmpz)2(PR3)2]: Synthesis and characterization

The reactions of [Pd2Ar2(μ-Cl)2(PR3)2] with pyrazole or 3,5-dimethylpyrazole in the presence of methanolic sodium hydroxide yield pyrazolato-bridged binuclear arylpalladium complexes, [Pd2Ar2(μ-pz′)2(PR3)2] (Ar=Ph or C6H4Me-4 (tol); pz′=pz or dmpz; PR3=PEt3, PMe2Ph). These complexes exist exclusively in sym-trans form both in solution (by NMR) and in the solid state (by X-ray). The molecular structures of [Pd2tol2(μ-Cl)2(PMe2Ph)2], [Pd2tol2(μ-pz)2(PMe2Ph)2] and [Pd2tol2(μ-dmpz)2(PEt3)2] have been established by X-ray diffraction analyses. The former is a centrosymmetric dimer while the latter two adopt a boat like conformation. The Pd⋯Pd separation in pyrazolato-bridged complexes is influenced by steric demands of particular pyrazolato-ligand.

Synthesis, Characterization and Anti-Diabetic Activity of 1,3,5-Triaryl-2-Pyrazolines in Acetic Acid Solution under Ultrasound Irradiation

A chalcone was prepared by the reaction of 4-methylbenzaldehyde with 4-methylacetophenone in dilute methanolic sodium hydroxide solution under ultrasonic irradiationin the water bath of an ultrasonic cleaner at room temperature. Treatment of this chalcone with thiosemicarbazide/semicarbazide hydrochloride/benzhydrazide/benzenesulphonyl hydrazide/phenylhydrazine hydrochloride afforded the corresponding 2-pyrazoline in good yields. All the new compounds have been characterized by IR, 1H-NMR, 13CNMR spectral data. All the target compounds were evaluated for their In Vivo anti-diabetic activity in rates in comparison with as reference drug.

Synthesis, Characterization and Anti-Diabetic Activity of 1,3,5-Triaryl-2-Pyrazolines in Acetic Acid Solution under Ultrasound Irradiation

A chalcone was prepared by the reaction of 4-methylbenzaldehyde with 4-methylacetophenone in dilute methanolic sodium hydroxide solution under ultrasonic irradiationin the water bath of an ultrasonic cleaner at room temperature. Treatment of this chalcone with thiosemicarbazide/semicarbazide hydrochloride/benzhydrazide/benzenesulphonyl hydrazide/phenylhydrazine hydrochloride afforded the corresponding 2-pyrazoline in good yields. All the new compounds have been characterized by IR, 1H-NMR, 13CNMR spectral data. All the target compounds were evaluated for their In Vivo anti-diabetic activity in rates in comparison with as reference drug.

Alkali Catalysis of Different Vegetable Oils for Comparisons of Their Biodiesel Productivity

The main advantages of biodiesel are its biodegradability, renewablity, improved nontoxic exhaust emissions and unnecessary alteration of common diesel engines. Today, biodiesel is produced by catalysis of inorganic acids, alkali and free or immobilized lipases with vegetable oil and short chain alcohols. Alkali and acidic catalysts are the most using catalysts for production of biodiesel because of their higher reaction yield and rate. In this study, we have comprised biodiesel productivity of different vegetable oils like sunflower, safflower, canola, soybean, olive, hazelnut, corn oils and waste sunflower oils by alkali catalysis. The transesterification of oils were performed by using NaOCH3 as catalyst at 25°C and at 100°C for 1 h. A defined amount of methanol as 6/1 molar ratio to oil was premixed with the metallic sodium. The amount of metallic sodium in methanol was 1.6 w% of oil mass for all of the crude oils/frying oil. Optimum reaction temperature was found as 25°C. TLC (Thin Layer Choromatography) image and GC (Gas Choromatography) results demonstrates that the dominant fatty acid in safflower, soy bean, sunflower, canola, corn and waste sunflower oil esters was linoleic acid (18:2). Besides it was oleic acid (18:1) for the olive and hazelnut oil esters. When biodiesel productivities of eight different oils were compared, similar results were obtained.