Poly[(2-Hydroxy-4-Methoxy Benzophenone) Butylene] Resin and its Polychelates with Lanthanides(III): Synthesis and Characterization

ABSTRACT

The resin (polymeric ligand) was prepared from 2-hydroxy-4-methoxy benzophenone with 1,4-butane diol in the presence of polyphosphoric acid as a catalyst at 160°C for 9 h. The poly[(2-hydroxy-4-methoxy benzophenone) butylene] L = H(HMBP-BD) form 1:2, ML₂, complexes with M = La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), and Dy(III). The polymeric ligand and its polychelates were characterized by elemental analyses, electronic spectra, and magnetic susceptibilities, IR-spectroscopy, NMR, and thermogravimetric analyses. The number average molecular weight (M¯n) of the resin was determined by Vapour Pressure Osmometry (VPO). All the polychelates are paramagnetic in nature. The resins and their polychelates were screened for their antimicrobial activity against E. coli, B. substilis, S. aureus (bacteria), and S. cerevisiae (yeast). It was found that the polychelates show good antimicrobial activity compared to the free polymeric ligand.     

A water-soluble Irgacure 2959-based diallylammonium salt system for antibacterial coatings

A water-soluble mixture of a novel diallylammonium salt photoinitiator based on 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (Irgacure 2959 or I2959) and diallylammonium tosylate has been prepared. It shows excellent water-solubility of 6.8 wt% in water, much greater than the solubility of I2959 (<2 wt%). It has a strong absorbance at 269 nm (ε ~ 15731) in methanol. It exhibits 15.6 times higher migration stability than I2959 due to its monomeric nature. Its photoinitiating efficiency of 2-hydroxyethylmethacrylate (HEMA) and poly(ethylene glycol) diacrylate (PEGDA, M_n = 575 D) was found to be similar to I2959. PEGDA hydrogels prepared using the synthesized photoinitiator (PI) were found to have highly porous structures (15.44 μm) compared with those using I2959. PEGDA film prepared using this PI has demonstrated antibacterial properties against gram-negative Pseudomonas aeruginosa (ATCC 15442) and gram-positive Staphylococcus aureus (ATCC 23235) bacterial species.     

p-Sulphonatocalix[8]arene functionalized silica resin for the enhanced removal of methylene blue from wastewater: equilibrium and kinetic study

ABSTRACT

The present investigation represents the synthesis of new p-sulphonatocalix[8]arene-based silica resin, p-SC8SR (5) and its application for the enhanced removal of methylene blue (MB) dye from contaminated water. The new p-SC8SR (5) resin was characterized by FT-IR, SEM, and EDX spectroscopy. The adsorption of MB on p-SC8SR (5) was investigated systematically by evaluating the effects of adsorbent dosage, initial pH, contact time, dye concentration, and ionic strength. Excellent adsorption (94%) of MB on p-SC8SR (5) was achieved at pH 9.5, contact time 10 min by using 0.2 mol L^?1 ionic strength and 2 × 10^?5 M initial MB dye concentration. Kinetic behavior of MB dye adsorption process on the newly synthesized p-SC8SR (5) adsorbent follows the pseudo-second-order rate model (R² = 0.998 and 0.999 for 2 × 10^?5 M and 1 × 10^?4 M, respectively). Adsorption isotherms were fitted well by the Freundlich model with excellent value of coefficient of determination (R²) = 0.995 which demonstrated that the adsorption of MB follows multilayer mechanism. Wastewater samples contaminated with MB were used to assess efficiency of the p-SC8SR (5) adsorbent. Results indicated that newly synthesized p-SC8SR (5) was found to be efficient adsorbent. During the removal process, the role of different functional groups’ cyclic structure was scrutinized and found that the ionic property as well as π–π interaction of host molecules played imperative role in the extent of adsorption.     

New Sphingolipids with a Previously Unreported 9-Methyl-C<Subscript>20</Subscript>-sphingosine Moiety from a Marine Algous Endophytic Fungus <Emphasis Type="Italic">Aspergillus niger</Emphasis> EN-13

Asperamides A (1) and B (2), a sphingolipid and their corresponding glycosphingolipid possessing a hitherto unreported 9-methyl-C₂₀-sphingosine moiety, were characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from marine brown alga Colpomenia sinuosa. The structures were elucidated by spectroscopic and chemical methods as (2S,2′R,3R,3′E,4E,8E)-N-(2′-hydroxy-3′-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (1) and 1-O-β-d-glucopyranosyl-(2S,2′R,3R,3′E,4E,8E)-N-(2′-hydroxy-3′-hexadecenoyl)-9-methyl-4,8-icosadien-1,3-diol (2). In the antifungal assay, asperamide A (1) displayed moderate activity against Candida albicans.     

2-Hydroxy-4-benzyloxylimine Resveratrol Derivatives as Potential Multifunctional Agents for the Treatment of Parkinson's Disease

A series of 2-hydroxy-4-benzyloxylimine resveratrol derivatives was designed, synthesized and evaluated as multifunctional agents for the treatment of Parkinson's disease. The results revealed that most derivatives possessed good multifunctional activities. Among them, representative compound (E)-5-[(4-fluorobenzyl)oxy]-2-{[(4-hydroxyphenyl)imino]methyl}phenol ( 7 h ) exhibited excellent MAO-B inhibition (IC₅₀=8.43×10⁻³ μM) and high antioxidant activity (ORAC=3.45 Trolox equivalent). Additionally, 7 h displayed good metal chelating ability, appropriate blood–brain barrier (BBB) permeability, significant neuroprotective effect, and great anti-neuroinflammatory activity. Furthermore, 7 h can also ameliorate 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-induced Parkinson's disease symptoms in mice. Therefore, compound 7 h was found to be a promising candidate for further development against PD.     

Synthesis,metal ion complexation and antibacterial activities of some thiapodands with lipophilic amide and ester end groups

A series of acyclic analogues of thiacrown ethers (podands) 7–12 with lipophilic amide and ester end groups were synthesized in high yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Podands 7 and 11 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Cd²⁺, Hg²⁺, Zn²⁺ and Pb²⁺ which begins to level off at a mole ratio of 1:1 podand to metal indicating the formation of a stable 1:1 complexes. On the other hand, podand 9 also showed the formation of 1:1 complexes with above metal cations except with Hg²⁺ ion, which formed a 1:2 podand-to-metal ratio complex. An influence of end groups on metal ion selectivity is evident. Podands having ethoxy end groups (podands 8, 10 and 12 exhibit pronounced metal ion selectivity over podands having amino end groups (podands 7, 9 and 11). Compounds 10 and 12 with dithiaethylene units and ethoxy end groups provide the best selectivity for Hg²⁺ and Ag⁺ ions. These results suggest that podands 10 and 12 could be useful for the selective removal of Hg²⁺ and Ag⁺ ions from industrial waste that may contain a variety of toxic heavy and transition metal ions. The in vitro antibacterial activity of the investigated compounds was tested against several microorganisms such as Bacillus subtilis (ATCC 6633), Micrococcus luteus (ATCC 10240), Staphylococcus aureus (ATCC 43300), Escherichia coli (ATCC 25922) and Enterobacter aerogenes (ATCC 13048). The antibacterial activity of podand 10 is significant for M. luteus and B. subtilis compared with other podands under investigation.     

A new route to steroid ring C aromatization from readily available precursors

3β-Acetoxy-8α,9α-epoxy-5α-cholest-14-ene (1); 3β-acetoxy-14α,15α-epoxy-5α-cholest-8-ene (2); 3β-acetoxy-5α-cholest-8(14)-ene-9α,15α-diol (3); and 3β-acetoxy-5α-cholesta-8(14),9(11)-dien-15α-ol (4) have been aromatized to a 9∶1 mixture of 3β-hydroxy-12-methyl-18-nor-5α,17β(H)-cholesta-8,11,13-triene (5a) and 3β-hydroxy-12-methyl-18-nor-5α,17α(H)-cholesta-8,11,13-triene (5b) in ethanol solution by using hydrochloric acid. The aromatization by action ofp-toluenesulfonic acid gave mainly the epimer with the natural C-17 configuration as the acetate 5c at the appropriatep-toluenesulfonic acid concentration. 3β-Acetoxy-5α-cholesta-7,9(11),14-triene (7a) and 3β-hydroxy-5α-cholesta-8,11,14-triene (8a), 2 intermediary compounds in the aromatization, were isolated and characterized.     

Effect of Trehalose and Drying Process on the Survival of Encapsulated Lactobacillus casei ATCC 393

Encapsulated Lactobacillus casei ATCC 393 was prepared by extrusion technology with rice shell powder and alginate followed by drying at 4°C. Drying at 4°C was beneficial to the survival of L. casei ATCC 393 compared with freeze drying. Trehalose had a positive effect on the survival of dried L. casei ATCC 393; the live cell numbers remained over 10⁷ cfu/g after 8 weeks of storage at 4°C. Survival of L. casei ATCC 393 decreased with the increase of relative humidity (from 33 to 97%) while the immobilization technique protected cells from adverse gastric conditions (pH 1.2) by the survival ratio of 89%.     

Isolation and structure of glucosylceramides from the starfish Cosmasterias lurida

From the water-insoluble lipid fraction of the methylene chloride/methanol extract of the starfish Cosmasterias lurida, two new glucosylceramides together with a known glucosylceramide, ophidiacerebroside E, were isolated by chromatographic procedures and characterized by spectroscopic (¹H and ¹³C nuclear magnetic resonance, mass spectrometry) methods. The new compounds were identified as (2S, 3R, 4E, 8E, 10E)-1-(β-d-glucopyranosyloxy)-3-hydroxy-2-[(R)-2-hydroxyheptadecanoyl)amino]-9-methyl-4,8,10-octadecatriene (3) and (2S,3R,4E,8E,10E)-1-(β-d-glucopyranosyloxy)-3-hydroxy-2-[(R)-2-hydroxyoctadecanoyl)amino]-9-methyl-4,8,10-octadecatriene (4).     

Microbial synthesis of chiral intermediates for β-3-receptor agonists

Chiral intermediates were prepared by biocatalytic processes for the chemical synthesis of β-3-receptor agonists. These include: (i) the microbial reduction of 4-benzyloxy-3-methanesulfonylamino-2′-bromoacetophenone 1 to the corresponding (R)-alcohol 2 by Spingomonas paucimobilis SC 16113. In the biotransformation process, a reaction yield of >85% and an optical purity of 99.5% were obtained for the desired (R)-alcohol 2; (ii) the enzymatic resolution of racemic α-methyl phenylalanine amide, 3, and α-methyl-4-hydroxy-phenylalanine amide, 5, by amidase from Mycobacterium neoaurum ATCC 25795 to prepare the corresponding (S)-amino acids 4 and 6. Reaction yields of 49.9 and 49 M% (theoretical maximum yield 50 M%) and optical purities of 99 and 94% were obtained for the desired (S)-amino acids 4 and 6, respectively; (iii) the asymmetric hydrolysis of methyl-(4-methoxyphenyl)-propanedioic acid, ethyl diester, 7, to the corresponding (S)-monoester 8 by pig liver esterase. A reaction yield of 96 M% and an optical purity of 96% were obtained for (S)-monoester 8 when reactions were carried out in a biphasic system containing 10% ethanol at 10°C.     

Male sex pheromone of cockroachEurycotis floridana (walker) (Blattidae,Polyzosteriinae): Role and composition of tergites 2 and 8 secretions

InEurycotis floridana, the male calling behavior is associated with the exposition of epidermal glands located under tergites 2, 7, and 8. 4-Hydroxy-5-methyl-3(2H)-furanone and 4-hydroxy-2,5-dimethyl-3(2H)-furanone were recently identified as the specific components of tergite 7 secretion. Methylene chloride extracts of tergite 7 and its major compound 4-hydroxy-5-methyl-3(2H)-furanone attract the conspecific females at a distance. Methylene chloride extracts of tergite 8 are also attractive at a distance to the females, whereas extracts of tergite 2 had no effect on males and females. Our GC investigations showed the absence of specific compounds in tergite 2 secretions. The GC-MS analyses revealed that the male secretion of the gland under tergite 8 is mainly a mixture of (2R*, 3R*)-butanediol, 1-dodecanol and benzyl 2-hydroxybenzoate. These compounds were tested at different concentrations on their own, or as a mixture. Only (2R*, 3R*)-butanediol and 1-dodecanol were attractive for the females. Their functions, as components of the male sex pheromone, in addition with the two derivatives of the furanone are discussed.     

Biostatic Behavior of Side Chain Charged Polycations and Polymer-Ag Complexes

Summary Poly[(3-methacryloylamino)propyl]trimethylammonium)chloride (PMF'TA), and poly (2-acrylamido-2-methyl-1-propane sulfonic acid) (PAPSA) were synthesized by radical polymerization. Three copolymers of (3-methacryloylamino)propyl] trimethylammonium chloride and 2-acrylamido-2-methyl-1-propane sulfonic acid P(MPTA-co-APSA) with different feed monomer mol ratios were also synthesized by radical polymerization. These polymer materials and the commercial poly(vinylpyrro1idone-co-2-dimethylaminoethyl methacrylate) quaternized P(VP-co- DMAEM) were purified by ultrafiltration membranes and subsequently their complexes with Ag(I) were prepared. Antibacterial activity of all these polymers, was investigated against Escherichia coli (6538P), and Staphylococcus aureus (ATCC 28922), using the National Comittee for Clinical Laboratory Standards method [1]. None of these compounds exhibited biocidal or biostatic action against E. coli, and only PMTA and P(VP-co-DMAEM) exhibited some action against S. aureus.     

Design,Synthesis, and Dual Evaluation of Quinoline and Quinolinium Iodide Salt Derivatives as Potential Anticancer and Antibacterial Agents

A series of novel quinoline and quinolinium iodide derivatives were designed and synthesized to discover potential anticancer and antibacterial agents. With regard to anticancer properties, in vitro cytotoxicities against three human cancer cell lines (A-549, HeLa and SGC-7901) were evaluated. The antibacterial properties against two strains, Escherichia coli (ATCC 29213) and Staphylococcus aureus (ATCC 8739), along with minimum inhibitory concentration (MIC) values were evaluated. The target alkyliodine substituted compounds exhibited significant antitumor and antibacterial activity, of which compound 8-((4-(benzyloxy)phenyl)amino)-7-(ethoxycarbonyl)-5-propyl-[1,3]dioxolo[4,5-g]quinolin-5-ium ( 12 ) was found to be the most potent derivative with IC₅₀ values of 4.45±0.88, 4.74±0.42, 14.54±1.96, and 32.12±3.66 against A-549, HeLa, SGC-7901, and L-02 cells, respectively, stronger than the positive controls 5-FU and MTX. Furthermore, compound 12 had the most potent bacterial inhibitory activity. The MIC of this compound against both E. coli and S. aureus was 3.125 nmol ⋅ mL⁻¹, which was smaller than that against the reference agents amoxicillin and ciprofloxacin.     

Two Novel Ceramides with a Phytosphingolipid and a Tertiary Amide Structure from <Emphasis Type="Italic">Zephyranthes candida</Emphasis>

Two novel ceramides, Candidamide A (1) with a phytosphingolipid structure, and Candidamide B (2) with a tertiary amide structure, together with 12 known compounds (3–14) have been isolated from the bulbs of Zephyranthes candida, The structures of 1 and 2 have been elucidated to be 1,3,5,6-tetrahydroxy-2-(2′-hydroxytetracosanoyl amino)-8-(E)-octadecadiene (1) and (2S,3S,4R,8E,2′R)-2-[N-(2′-hydroxyoctadecanoyl)-N-(1′′,2′′-dihydroxyethyl)-amino]-8-hexacosene-1,3,4-triol (2) on the basis of spectroscopic evidence including IR, MS, NMR (¹H-NMR, ¹³C-NMR, DEPT, ¹H–¹H COSY, HSQC, HMBC). The known compounds were identified as (2S)-3′,7-dihydroxy-4′-methoxyflavan (3), (2S)-4′-hydroxy-7-methoxyflavan (4), (2S)-4′,7-dihydroxyflavan (5), 7-hydroxy-3′, 4′-methylenedioxyflavan (6), ambrettolide (7), β-sitostero1 (8), β-daucosterin (9), rutin (10), pancratistatin (11), lycorine (12), haemanthidine (13), and haemanthamine (14). In the antimicrobial assay, candidamide A (1) and candidamide B (2) displayed moderate activities against bacteria Staphylococcus aureus and Escherichia coli, and fungi Aspergillus niger, Candida albicans and Trichophyton rubrum.     

A Highly Permeable Membrane for Separation of Quercetin Obtained by Nickel(II) Ion-Mediated Molecular Imprinting

A polymer membrane imprinted with quercetin has been synthesized in the presence of nickel(II) acetate as a metal ion mediator. A mixture of methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), tetrahydrofuran (THF) – methanol (3:1 v/v) as a solvent and Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one) as a photoinitiator was polymerized on a track-etched membrane (pores 0.4 µm) used as a support. The polymer formed regular layers on both sides of the membrane and filled the pores. The highest initial flux of the template of 1.8 · 10^?7 mol · cm^?2 · h^?1 was observed for its diffusion from THF/acetate buffer (20:80, v/v) into THF. Membranes polymerized with nickel(II) were both more permeable and more selective. The maximum selectivity factors, calculated by using percent permeation, were 4.5 (quercetin/rutin) and 4.9 (quercetin/naringenin).     

Polyaniline membranes for nanofiltration of solvent from dewaxed lube oil

Polyaniline nanofiltration membranes were synthesized to examine a potential candidate for application of solvent recovery from lube oil. An integrally skinned polyaniline membrane was cast on a woven polyester fabric and then was chemically crosslinked with glutaraldehyde in order to further increase the membranes resistant in a methyl ethyl ketone and toluene mixture. Subsequently, membrane performance was tested under different operational conditions. The operation pressure was fixed at 35 bar and was held constant for all of the tests. The membrane demonstrated a permeate flux of 10 l/(m² h) and oil rejection of 69%.

Abbreviations: PANi: Polyaniline; PI: polyimide; MEK: methyl ethyl ketone; GA: glutaraldehyde; NMP: N-methyl-2-pyrrolidone; 4MP: 4-methylpiperidine; SEM: Scanning Electron Microscope; OSN: organic solvent nanofiltration; MWCO: molecular weight cut-off.     

Chromatographic fractionation of lithium isotope in aqueous solution using bifunctional ion-exchange resin

ABSTRACT

We have examined the effect of bifunctional group in the same cross-linkage degree on the Li isotope fractionation in the cation exchange reaction in the aqueous solutions ranging in temperature from 278 to 333 K. For this purpose, the sulfonated pyridine-styrene-divinylbenzene resin with the cross-linkage degree of 50 wt%, embedded in porous silica beads was successfully synthesized by a typical polymerization method. The isotope separation coefficients (ε) per unit mass (ε/ΔMass) was 8.1 × 10^–4 at 298 K. Therefore, the effect of bifunctional group against the ε/ΔMass value has been discussed, compared with those of previous works.     

Two novel glucosylceramides from gonads and body walls of the Patagonian starfish Allostichaster inaequalis

From the water-insoluble lipid fraction of the chloroform/methanol/water extract of the gonads and body walls of the Patagonian starfish Allostichaster inaequalis, two new glucosylceramides (4 and 7) were isolated together with the known phalluside-1 (1) and two glucosylceramides (2 and 3) previously isolated from the starfish Cosmasterias lurida. The new compounds were characterized as (2S,3R,4E,8E,10E)-1-(β-d-glucopyranosyloxy)-3-hydroxy-2-[(R)-2-hydroxy-15-tetracosenoyl] amino-4,8,10-octadecatriene (4) and (2S,3R,4E,15Z)-1-(β-d-glucopyranosyloxy)-3-hydroxy-2-[(R)-2-hydroxyhexadecanoyl] amino-4,15-docosadiene (7) by means of spectroscopic and chemical methods.     

Separation and Purification of Quinolone Alkaloids from the Chinese Herbal Medicine Evodia rutaecarpa (Juss.) Benth by High Performance Counter-Current Chromatography

Preparative separation of quinolone alkaloids in Evodia rutaecarpa (Juss.) Benth was conducted by high performance counter-current chromatography (HPCCC) with a pair of two solvent systems consisting of n-hexane-methanol-water-acetic acid (2:1:1:0.2, v/v) and (5:4:2:0.1, v/v). Consequently, 31.78 mg 1-methyl-2-nonyl-4 (1H)-quinolone (I), 59.25 mg 1-methyl-2-(6-undecenyl)-4 (1H)-quinolone (II), 333.27 mg evocarpine (III), 101.13 mg 1-methyl-2-(6,9-pentadecadienyl)-4(1H)-quinolone (IV), 132.17 mg dihydroevocarpine (V), and 86.99 mg 1-methyl-2-(10-pentadecenyl)-4(1H)-quinolone (VI) were obtained from 1.3 g of the crude extract. The structures of these compounds were identified by mass spectrometer (MS), nuclear magnetic resonance (¹H NMR and ¹³C NMR).     

Facile synthesis of novel 6-methyl-5-phenyl-2-sulfido-1,2,3,5-tetrahydro-4H[1,2] oxazolo[4′,5′:5,6]pyrano[2,3-d][1,3,2]diazaphosphinines

A number of 6-methyl-5-phenyl-2-sulfido-1,2,3,5-tetrahydro-4H[1,2]oxazolo[4′,5′: 5,6]pyrano[2,3-d][1,3,2]diazaphosphinines 4–11 were synthesized via an interaction of tetraphosphorus decasulfide and Lawesson’s reagent under different conditions with 6-amino-3-methyl-4-phenyl-4H-pyrano[3,2-d][1,2]oxazole-5-carbonitrile (3). The reaction mechanisms for these products were discussed. Structures of the newly synthesized products were established on the basis of elemental analysis and spectral data.