Synthesis and Spectroscopic Properties of a Covalently Linked Porphyrin–Fullerene C60 Dyad

A covalently linked porphyrin–fullerene C₆₀ dyad 6 was conveniently synthesized by 1,3‐dipolar cycloaddition using 5‐(4‐carbonylphenyl)‐10,15,20‐tris(4‐methoxylphenyl)porphyrin 5, N‐methylglycine and fullerene C₆₀. Spectroscopic studies show that dyad 6 is a promising architecture with potential application as photoactive organic material.     

Synthesis of a Novel Organic Soluble and Thermal-stable Fullerene-perylene Dyad

A novel organic soluble and thermal-stable fullerene-perylene dyad, in which a perylenemoietyis attached to C60, has been prepared by 1, 3-dipolar cycloaddition of the azomethine ylidesgenerated in situ from the aldehyde and N-methylglycine and characterized by NMR, FT-IR, TGA,absorption and fluorescent spectra etc.     

A Convenient Synthesis of Novel Meldrum＇s Acid C60 Fullerene Derivatives

A series of novel Meldrum＇s acid C60 derivatives were prepared in moderate yields from a convenient one-pot reaction of C60, the Meldrum＇s acid derivatives, 12 and 1,8-diazabicyclo-[5,4,0]-undec-7-ene （DBU） in toluene at room temperature under nitrogen atmosphere. All the new compounds were fully characterized by the spectral data and elemental analysis. A carbene intermediate mechanism was proposed for this reaction.     

Preparation and some properties of ionic salts of C 60 − and C 60 2− fullerides with phthalocyanine cations

Ionic fullerides of C ₆₀ ^? and C ₆₀ ^2? with the silicon phthalocyanines cations were obtained in the reaction of PcSi(OH)₂ with fullerene C₆₀ in the presence of KOH in DMSO or in xylene and THF with the addition of 15C5 crown ether. The fullerides were characterized by electron absorption, ¹H NMR and electron spin resonance spectra, and their reaction with O₂ and CF₃COOH were carried out.     

Novel Role of Carbon Dioxide as a Selective Agent in Palladium-Catalyzed Cyclotrimerization of Alkynes

Carbon dioxide was found as a selective agent to promote the palladium-catalyzed cyclotrimerization of alkynes in water. Both aryl and alkylacetylenes afforded the corresponding cyclotrimerization products regioselectively in high yields using PdCl2, CuCl2, and CO2 as the catalytic system. However, tert-butylacetylene bearing a bulky group gave a dimerization product. Mechanism of this reaction was also discussed.     

Fullerene C60 as a η5- and η6-ligand in sandwich-type π-complexes with transition metals

The molecular and electronic structures of some hypothetical sandwich-type -complexes of transition metals with fullerene C₆₀ were modeled. The M-C₆₀ bonds in ⁵-C₆₀MCp⁺ complexes (M = Fe, Ru, Os) are less strong than the M-Cp bonds in ferrocene, ruthenocene, and osmocene, respectively. The ⁶-C₆₀MC₆H₆ complexes (M = Cr, Mo, W) should be less stable than their classical analogs (C₆H₆)M(C₆H₆). The coordination of a metal atom with the fullerene at its pentagonal face is more energetically favorable than at a hexagonal face.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 598–601, April, 1994.We are grateful to V. I. Sokolov for discussion of the results obtained. This study was supported by the Russian Foundation for Basic Research (grants 93-03-4101 and 93-03-18725).     

Design of Chiral NHC-Carboxylates as Potential Ligands for Pd-Catalyzed Enantioselective C−H Activation

Despite numerous efforts, the synthesis of scalemic carbo- and heterocycles through Pd⁰-catalyzed C(sp³)−H activation employing chiral ancillary ligands or chiral bases is still limited. Inspired by the recently reported outstanding performance of IBiox-type NHC ligands and bifunctional ligands in similar transformations, a new class of bifunctional NHC-ligands bearing a pendant carboxylate group was designed. A library of 10 imidazolium-carboxylic acids was obtained in five to six steps from enantiopure l -tert-leucinol. In addition, four well-defined Pd(DMBPA)-NHC palladacycles were synthesized in good to excellent yields from the corresponding imidazolium precursors. These complexes were tested in a prototypical C(sp³)−H arylation reaction, and the most active one afforded the indoline product in low yield but significant enantioselectivity. These new bifunctional NHCs could find broader applications in catalytic enantioselective transformations occurring under milder conditions.     

Synergistic Effect of Phosphite with FuUerene C60 and Fullerenol C60（OH）24 as Antioxidants in Polypropylene

Polypropylene samples with fullerene C60, fullerenol C60（OH）24, 1010, C60/168, C60-OH/168 and 1010/168 as antioxidants were prepared by extrusions. MFR, YI, TGA and OIT of all the samples were tested. According to the results of MFR, during the melt extrusion, fullerene showed excellent stability effect on PP. The antioxidative ability of fullerene was comparable to the traditional antioxidant 1010. The antioxidative ability of fullerenol was not significant in the first extrusion and it accelerated the degradation of PP in the second and the third extrusions. TGA and OIT tests showed that the stability effects of fullerene and fullerenol were slightly lower than antioxidant 1010. In the first time, antioxidant 168 was reported to show great synergistic effects with fullerene and fullerenol as antioxidants, which sussested a simple way to enhance the antioxidative abilities of fullerene and fullerenol.     

Silica Chromate as a Novel Oxidizing Agent for the Oxidation of 1,4‐Dihydropyridines

Silica chromate easily converts 1,4‐dihydropyridines to their corresponding pyridines in the presence of NaHSO₄ · H₂O and wet SiO₂ in dichloromethane at room temperature in good to excellent yields.     

Paraplantaricin L-ZB1, a Novel Bacteriocin and Its Application as a Biopreservative Agent on Quality and Shelf Life of Rainbow Trout Fillets Stored at 4 °C

Paraplantaricin L-ZB1 was produced by Lactobacillus paraplantarum L-ZB1, which was isolated from the traditional China fermented sausage. In this work, paraplantaricin L-ZB1 was used to maintain quality of rainbow trout fillets at 4 °C. Rainbow trout fillets were left untreated (CK) or treated with 200 activity units (AU)/ml paraplantaricin L-ZB1 (P1), 400 AU/ml paraplantaricin L-ZB1 (P2) or 200 AU/ml Nisin (N). The treated samples were stored at 4 °C for up to 10 days, and the quality changes were determined by microbiological (total viable count [TVC], Enterobacteriaceae, Pseudomonas, spore-forming bacteria), sensory, chemical (pH, total volatile basic nitrogen [TVB-N]) and biochemical (biogenic amines, K value) methods. Results show that paraplantaricin L-ZB1 could inhibit the growth of microflora, especially Enterobacteriaceae, Pseudomonas and spore-forming bacteria during sample storage. Meanwhile, the increases of pH, TVB-N, K value and biogenic amine levels were significantly delayed in paraplantaricin L-ZB1-treated samples compared to the control group. Paraplantaricin L-ZB1 of 400 AU/ml extended the rainbow trout fillets’ shelf life to 4–6 days, and the sample showed good sensory characteristics. Therefore, paraplantaricin L-ZB1 could be used as a suitable biological preservative for chilled rainbow trout fillets.     

Transition-Metal-Free Coupling of 1,3-Dipoles and Boronic Acids as a Sustainable Approach to C−C Bond Formation

The need for alternative, complementary approaches to enable C−C bond formation within organic chemistry is an on-going challenge in the area. Of particular relevance are transformations that proceed in the absence of transition-metal reagents. In the current study, we report a comprehensive investigation of the coupling of nitrile imines and aryl boronic acids as an approach towards sustainable C−C bond formation. In situ generation of the highly reactive 1,3-dipole facilitates a Petasis–Mannich-type coupling via a nucleophilic boronate complex. The introduction of hydrazonyl chlorides as a complementary nitrile imine source to the 2,5-tetrazoles previously reported by our laboratory further broadens the scope of the approach. Additionally, we exemplify for the first time the extension of this protocol into another 1,3-dipole, through the synthesis of aryl ketone oximes from aryl boronic acids and nitrile N-oxides.     

Synthesis, Crystal Structure and Antimicrobial Activity of a Novel Ni(Ⅱ) Complex

A new nickel(Ⅱ) complex, C34H38N8NiO4, has been prepared and charac-terized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 11.715(5), b = 12.328(5), c =11.113(5) A, β= 92.589(5)°, Z = 2, Dc = 1.411 g/cm3, μ = 0.658 mm-1, the final R = 0.0427 and wR = 0.1099 for 2229 observed reflections with Ⅰ> 2σ(Ⅰ). The complex is a centrosymmetric plane in which nickel(Ⅱ) is coordinated in a regular octahedron to the ligand phenytoin through the nitrogen atoms of ethylenediamine, imine and amine. The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method, and found to be active against the four test bacterial organisms. Preliminary screening for antimicrobial activities showed that the title complex is quite active against standard strains of Salmonella species, Staphylococcus aureus, Bacillus pumilus and Eschierichia coli.     

Synthesis, Crystal Structure and Antimicrobial Activity of a Novel Ni(II) Complex

A new nickel(II) complex, C34H38N8NiO4, has been prepared and charac- terized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 11.715(5), b = 12.328(5), c =11.113(5) , β = 92.589(5)°, Z = 2, Dc = 1.411 g/cm3, μ = 0.658 mm-1, the final R = 0.0427 and wR = 0.1099 for 2229 observed reflections with I > 2σ(I). The complex is a centrosymmetric plane in which nickel(II) is coordinated in a regular octahedron to the ligand phenytoin through the nitrogen atoms of ethylenediamine, imine and amine. The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method, and found to be active against the four test bacterial organisms. Preliminary screening for antimicrobial activities showed that the title complex is quite active against standard strains of Salmonella species, Staphylococcus aureus, Bacillus pumilus and Eschierichia coli.     

Synthesis,Crystal Structure and Antimicrobial Activity of a Novel Ni（Ⅱ） Complex

A new nickel（Ⅱ） complex, C34H38N8NiO4, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/c with a = 11.715（5）, b = 12.328（5）, c =11.113（5）A, β= 92.589（5）°, Z = 2, Dc = 1.411 g/cm^3,μ = 0.658 mml, the final R = 0.0427 and wR = 0.1099 for 2229 observed reflections with I 〉 2σ（I）. The complex is a centrosymmetric plane in which nickel（Ⅱ） is coordinated in a regular octahedron to the ligand phenytoin through the nitrogen atoms of ethylenediamine, imine and amine. The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method, and found to be active against the four test bacterial organisms. Preliminary screening for antimicrobial activities showed that the title complex is quite active against standard strains of Salmonella species, Staphylococcus aureus, Bacillus pumilus and Eschierichia coli.     

Synthesis of Mesoporous Lanthanum Phosphate and Its Use as a Novel Sorbent

Mesoporous lanthanum phosphate was synthesized by supramolecular self-assembly of cetyltrimethylammo-nium bromide and lanthanum nitrate following digestion in phosphoric acid.TGA-DTA,XRD and SEM were em-ployed to study the uncalcined and calcined materials.Sorption behavior of Cr(Ⅲ),Mn(Ⅱ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ),Cd(Ⅱ),Ba(Ⅱ),Hg(Ⅱ)and Pb(Ⅱ)cations was studied on such materials in water,3 mol·L~(-1)ammonia,0.01 mol.L~(-1)potassium ferrocyanide and 0.01 mol·L~(-1)potassium ferricyanide solutions.     

Synthesis and Antimicrobial Activity of Novel Types of Persulfide-Spacer α-O-glycosides: Formation of a Super Hydrophobic Layer via a Self-Organization Effect Through the Strong Hydrogen Bonding Interaction

We report the synthesis of new polyether-based polyols derived from carbohydrates carrying a thioether-spacer in the attempt to potentially provide new antibiotics. The monosaccharide cores are based on d-galactose, d-mannose and d-glucose and the spacer are being built by allylation of the free hydroxyl groups followed by the radical addition of 2-mercaptoethanol using a radical initiator. The CI-MS analysis demonstrated the stepwise and successive fission of the sulfide-spacer groups, however, it did not distinguish between sugars having different arrangement of O-(CH₂)₃-S(CH₂)₂OH groups. The SEM image of methyl 2, 3, 4, 6-tetra-O-[3-(hydroxythioethyl)-propyl]-α-d-mannopyranoside, as a representative example, demonstrated a super hydrophobic layer formed via a self-organization effect through the strong hydrogen bonding interactions of the spacer groups. To the best of our knowledge, this is the first report on the formation of such rough surface nanostructure layer from simple monosaccharide. The investigated compounds exhibited antimicrobial activity against the two tested gram-negative bacteria, E. coli, Pseudomonas and the tested fungus Candida albicans at a concentration of 1 mg/cm³ dissolved in DMF. No antimicrobial activity against the tested gram-positive bacterium, S. aureus was detected.     

Directing Group-Promoted Inert C−O Bond Activation Using Versatile Boronic Acid as a Coupling Agent

A simple Ni(cod)₂ and carbene mediated strategy facilitates the efficient catalytic cross-coupling of methoxyarenes with a variety of organoboron reagents. Directing groups facilitate the activation of inert C−O bonds in under-utilized aryl methyl ethers enabling their adaptation for C−C cross-coupling reactions as less toxic surrogates to the ubiquitous haloarenes. The method reported enables C−C cross-coupling with readily available and economical arylboronic acid reagents, which is unprecedented, and compares well with other organoboron reagents with similarly high reactivity. Extension to directing group assisted chemo-selective C−O bond cleavage, and further application towards the synthesis of novel bifunctionalized biaryls is reported. Key to the success of this protocol is the use of directing groups proximal to the reaction center to facilitate the activation of the inert C−OMe bond.     

Molecular Iodine as a Versatile Reagent for the Synthesis of Thiazoloquinoline—A Potential Antibacterial Agent

Abstract

A series of 3-(2-aminothiazol-4-yl)quinolin-2[1H]-ones 3 was prepared by neat reaction of quinolin-2[1H]-ones 1 with thioureas 2 in the presence of molecular iodine. The synthesized compounds were evaluated for their in vitro antimicrobial activities against Escherichia coli, Paedococcus sp., Lactobacillus, Yersinia enterocolitica, and Staphylococcus aureus. The green chemical approach for the synthesis of thiazoloquinolinone 3 was performed under neat conditions using molecular iodine as catalyst as well as reaction medium.

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GRAPHICAL ABSTRACT      

Exohedral Addition Chemistry of the Fullerenide Anions C602− and C60⋅−

A systematic screening study of the exohedral reactivity of the reduced fullerenes (fullerenides) C₆₀²⁻ and C₆₀^⋅− is reported. These doubly and singly negatively charged carbon cages were prepared by two-fold reduction of C₆₀ with potassium, leading to K₂C₆₀, or by in situ monoreduction with the radical anion of benzonitrile PhCN^⋅−, respectively. Several series of electrophiles, including geminal and distant dihalides, benzyl bromides, and diazonium compounds, were employed as addition partners. In general, the investigated bromides proved to be the most suitable reaction partners. A series of fullerene adducts and cycloadducts involving either 1,2- or 1,4-addition patterns, depending on the precise architecture and the steric demand of the addends, were synthesized and fully characterized. Some of the reaction products are unprecedented and inaccessible forms of neutral C₆₀. The fullerenide chemistry presented here closely resembles related reactions of graphenides and carbon nanotubides, which are the most powerful methods for the functionalization of these macromolecular forms of synthetic carbon allotropes (SCAs). Activation of C₆₀ by negative charging represents a little explored concept of fullerene chemistry, providing both new insights of fullerene reactivity itself and new types of exohedral derivatives.     

Effect of Cl−, Br− and I− ions on the adsorption and association of cytosine at a mercury electrode

The pit, on alternating current polarograms of bases, indicating the region of potentials where the association of the adsorbed molecules takes place and a compact surface film is formed usually appears near the potential of the electrocapillary maximum. An exception in this respect is cytosine, which forms the pit at more negative potentials.The negative pit corresponds to the surface film formed by molecules of cytosine adsorbed electro- statically at the negatively charged mercury surface via their positive charge or the electropositive site. In the presence of Br⁻ or I⁻ ions the association of cytosine occurs also near the potential of the electrocapillary maximum. The I⁻ ions allow association at the electrically neutral electrode surface to occur more easily than do the Br⁻ ions. The surface film at the neutral electrode surface is formed by molecules of a complex of Br-cytosine, and/or I-cytosine. This complex has a higher surface activity than cytosine alone, due to the high polarizability of the bromine or iodine atoms, and the maximum adsorption is thus observed near the potential of the electrocapillary maximum, in a similar way as with 5-Br-cytosine or 5-I-cytosine.