Synthesis of β-fluoroenones and their reductive rearrangement in aqueous media

In this paper, a simple and efficient preparation of β-fluoroenones, as a mixture of E/Z isomers with the E-isomer as the main product, from 1,2-allenic ketones by using TBAF·3H₂O in water as a nucleophilic fluorination agent has been developed. Moreover, in exploring the synthetic applications of β-fluoroenones, an unprecedented reductive defluorination rearrangement of β-fluoroenones toward enones under mild conditions in aqueous media was also discovered.     

Sequence and linker dependent chiral dimerization of DNA–porphyrin conjugates

Circular dichroism (CD), UV–vis absorption, fluorescence, and resonance light scattering (RLS) spectroscopies were used to elucidate the role of the DNA sequence, linkers between DNA and porphyrin, and metal in the porphyrin coordination center on the self-assembly of DNA–porphyrin conjugates. A series of eight non-self-complementary DNA–porphyrin conjugates have been synthesized with zinc and free-base porphyrins covalently attached to the short ODNs (A₈ or T₈) via amide or phosphate linker. A small structural modification (e.g., amide linker replaced by the phosphate linker) showed a dramatic effect on the aggregation properties of DNA–porphyrin conjugates and greatly altered their spectroscopic properties. At low ionic strength, porphyrin aggregation was not observed for any conjugate. An increase in the ionic strength caused two out of eight conjugates to form chiral porphyrin dimers.     

Synthesis of β-cyclodextrin-lysozyme conjugates and their physicochemical and biochemical properties

Recently a great interest in the field of protein engineering and the design of innovative drug delivery systems employing specific ligands such as cyclodextrins is observed. The paper reports the solid state, thermal method for protein coupling with β-cyclodextrin and the physicochemical and biological properties of the obtained conjugates. The structure of the obtained conjugates was investigated via liquid chromatography-mass spectrometry, dynamic light scattering and circular dichroism analysis. The presented conjugates were biologically active and covalently bound β-cyclodextrin preserved the ability to form inclusion complexes with the model compound. This report demonstrates the great potential of cyclodextrin as a modifying unit that can be used to modulate the properties of therapeutic proteins, additionally giving such conjugates the possibility to transport many therapeutic substances in the form of inclusion complexes. In addition, the paper presents the potential of protein-cyclodextrin conjugates to construct innovative bioactive molecules for biological and medical applications.     

Intermolecular interaction between squarylium cyanine and porphyrin

In this paper, the interaction between squarylium cyanine and porphyrin in chloroform is investigated by absorption and fluorescence spectroscopy. Emphasis has been put on the mechanism of intermolecular energy transfer. The overlap integral J between the absorption spectrum of squarylium cyanine and the fluorescence spectrum of porphyrin was calculated, which reveals that the singlet-singlet energy transfer may occur from porphyrin to squarylium cyanine in solution. In comparison of the observed rate constant [kqII=6.1 ×1013 (mol/L)-1·s-1] for fluorescence quenching of porphyrin by squarylium cyanine with the diffusion rate constant in chloroform [kdif=1.1×1010 (mol/L)-1·s-1] and the rate of energy transfer [ket≤6.7×104 (mol/L)-1·s-1 in the experimentally dilute solutions] estimated from Forster formula, the possibility of energy transfer by electron exchange or/and coulombic mechanism could be excluded. So it has been definitely convinced that the intermolecuiar energy transfer between them is     

Antimicrobial activity of new carboxymethyl chitosan–carbon nanotube biocomposites and their swell ability in different pH media

New carboxymethyl chitosan–carbon nanotube (CMCS-CNT) biocomposites were prepared and characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and normal photography. The recorded images of the CMCS-CNT biocomposites showed homogeneous distribution of carbon nanotubes into the carboxymethyl chitosan (CMCS) matrix. Their antimicrobial activity and swell ability in different pH media have been investigated. They showed a higher antimicrobial activity against tested gram-positive and gram-negative bacteria. The inhibition zone diameters are closer to that recorded for the commonly used antibiotics. They showed an increase in the swell ability in different pH media relative to the parent CMCS. It would be expected that these nanobiocomposites are promising candidates for medical applications.     

Synthesis,antioxidant and anticancer screenings of berberine–indole conjugates

Research on Chemical Intermediates - A variety of heterocyclic nitrogen cores in the form of indole moieties were linked to the natural isoquinoline alkaloid molecule berberine to achieve...     

Synthesis and properties of covalently linked BF2–oxasmaragdyrin–porphyrin dyads and triad

Two covalently linked diphenyl ethyne bridged unsymmetrical dyads containing porphyrin and BF₂–oxasmaragdyrin and Zn(II)porphyrin and BF₂–oxasmaragdyrin units and one covalently linked triad containing Zn(II)porphyrin, porphyrin and BF₂–oxasmaragdyrin units were synthesized by coupling appropriate functionalized macrocycles under Pd(0) coupling reaction conditions. The dyads and triad were freely soluble in common organic solvents and confirmed by ES-MS spectra. 1D and 2D NMR techniques were used to characterize the dyads and triad. Absorption and electrochemical studies of dyads and triad showed the overlapping features of the constituted macrocycles indicating that the macrocycles retain their basic features in the dyads and triad. The BF₂–oxasmaragdyrin absorbs at lower energy and emits strongly in the visible region compared to porphyrin/Zn(II)porphyrin. Thus, BF₂–oxasmaragdyrin acts as energy acceptor and porphyrin/Zn(II) porphyrin act as energy donor in dyads and triad. The steady state and time-resolved fluorescence studies supported an efficient energy transfer from porphyrin/Zn(II)porphyrin to BF₂–oxasmaragdyrin unit in dyads and triad.     

Synthesis,spectroscopic, structural and magnetic studies of new binary Cr(III)–citrate pH-specific structural variants from aqueous media

In an attempt to understand the aqueous interactions of Cr(III) with the low molecular mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)–citrate system was pursued, leading to the new complexes Na₃[Cr(C₆H₅O₇)₂]·8.5H₂O (1) and (Hdmphen)₆[Cr(C₆H₅O₇)₂]·(NO₃)₃·14H₂O (2). Complexes 1 and 2 were characterized by elemental analysis, spectroscopic, structural, thermal, and magnetic susceptibility studies. The structures of 1 and 2 reveal a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. Albeit of the same deprotonation state, the disposition of the two citrate ligands with respect to Cr(III) differs between 1 and 2 in the solid state, thus reflecting the presence of pH-structural variants in the requisite binary system. This conformational difference is lifted in aqueous solution, thus providing (a) comparative information on the distribution and diversity of species in the binary Cr(III)–citrate system, and (b) insight into the nature of interactions developing in the binary Cr(III)–hydroxycarboxylate systems in abiotic and biological applications.     

Synthesis of a new β-naphthothiazole monomethine cyanine dye for the detection of DNA in aqueous solution

Novel monomethine cyanine dye (MC) derived from β-naphthothiazole and benzothiazole has been prepared and characterized by ¹H and ¹³C NMR, FTIR, ESIMS, elemental analyses, absorption and fluorescence spectroscopy. The dye was conveniently synthesized by the condensation of two sulfate heterocyclic quaternary salts. The interaction between calf thymus DNA (ct-DNA) in tris(hydroxymethyl)aminomethane–HCl (Tris–HCl) aqueous buffer solution and MC has been studied with spectral fluorescence method. The binding constant value has been determined by fluorescence titration of MC with ct-DNA concentrations. The result obtained is consistent with an intercalative binding interaction between MC and ct-DNA. Compared with ethidium bromide (EB), MC showed a huge fluorescence enhancement upon mixing with ct-DNA.     

Synthesis of functionalized core-modified sapphyrins and covalently linked porphyrin–sapphyrin dyads

We adopted simple synthetic strategy to synthesize mono-functionalized thiasapphyrins containing functionalized aryl group in the meso-position at thiophene side. The thiasapphyrin building block containing iodophenyl functional group was coupled with three different porphyrin building blocks with N₄, N₃S and N₂S₂ cores containing meso-ethynylphenyl functional group under mild Pd(0) coupling conditions to synthesize three covalently linked diphenyl ethyne bridged porphyrin–thiasapphyrin dyads. The porphyrin–thiasapphyrin dyads were characterized by mass, NMR, absorption, electrochemical and fluorescence techniques. The NMR, absorption and electrochemical studies indicated that the two components in dyads interact weakly and retain their individual identities. The steady state fluorescence studies indicated that the porphyrin fluorescence is reduced to a significant extent because of energy and/or electron transfer to the thiasapphyrin unit. The protonation studies indicated that N₄ porphyrin unit is more basic, whereas N₃S and N₂S₂ porphyrin units are less basic compared to thiasapphyrin unit in respective dyads. We explored the potential of dyads as fluorescent anion sensors and showed that two out of three dyads can be used as fluorescent anion sensors.     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Synthesis and light absorption of benzotellurazole crown ether cyanine dye

Various methods for synthesis of 2-methyl-5,6-(1,4,7,10,13-pentaoxatridecamethyl-ene)benzotellurazole (8) are described. Under different conditions, alkylation of compound 8 with methyl iodide gave telluronium salt 1,2-dimethyl-5,6-(1,4,7,10,13-pentaoxatridecamethylene)benzo-tellurazolium iodide (15) or quaternary ammonium salt 2,3-dimethyl-5,6-(1,4,7,10,13-pentaoxatri-decamethylene)benzotellurazolium iodide (14) in high yields, repectively. The cyanine dye 3,3'-dimethyl-5,6,5',6'-bis(1,4,7,10,13-pentaoxatridecamethylene)telluracarbocyanine iodide (16) is obtained by condensation of 14 with ethyl orthoformate in acetic anhydride. The visible absorption of the cyanine dye is also discussed.     

Synthesis and properties of polyfluorene copolymers bearing thiophene and porphyrin

To search for more wider absorption and higher charge carriers mobilities materials of polymer solar cell, a series of soluble alternating polyfluorene copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. Their structures were determined by 1H NMR, IR and UV-vis. And their UV-vis absorption spectra indicated that they had strong absorption over 600 nm spectral range and nearly cover 400-700 nm visible region. The band gaps of copolymers calculated according to cyclic voltammetry （CV） were between 1.96 and 2.03 eV. Polymer：TiO2 bulk-heterojunction films were made from mixtures of polymer and titanium isopropoxide, a precursor for TiO2, via hydrolysis in air overnight. The photoluminescence at 380-800 nm of the blend film of PT-TPP20 （5 mg/mL）：Ti（OC3H7）4 （80 μL/mL） （20% volume fraction） was significantly quenched in the 50% Ti（OC3H7）4 blend film, indicating that rapid and efficient separation of photoinduced electron-hole pairs.     

Synthesis of 6,8-dichloroquinolones utilizing new method and evaluation of their antibacterial activities

Several 6,8-dichloroquinolone analogues were synthesized from the key intermediate compound of 2,3,4,5-tetrachlorobenzene carbonyl chloride,which was obtained from the starting material of tetrachlorophthalic anhydride.Their in vitro antibacterial activities were evaluated.As a result of this study,compounds 21c and 21d were twofold more potent than ciprofloxacin (CPFX) and norfloxacin (NFLX) against Staphylococcus aureus-9,and with the same potent as CPFX and NFLX while against Escherichia coli-2,but were less potent than references in against Pseudomonas aeruginosa-17.     

Cycloaddition to a C3-ethynylated chlorophyll derivative and self-aggregation of zinc chlorin–pyrazole/triazole conjugates

Several kinds of cycloaddition reactions were applied to C3-ethynylated pyropheophorbide-a methyl ester to develop C3-functionalized chlorophyll derivatives. Its [2+2] cycloaddition with tetracyanoethylene, [2+3] cycloaddition with diazomethane, [2+3] Huisgen reaction with trimethylsilyl azide, and [2+4] Diels–Alder reaction with tetraphenylcyclopentadienone gave the expected products in moderate to high yields. Zinc complex of the resulting 3-pyrazolyl-chlorin was found to show self-aggregation in a less polar solvent, in an aqueous micelle, and in the solid thin films more readily than the corresponding zinc 3-triazolyl-chlorin.     

Synthesis of new potential chelating agents: Catechol–bisphosphonate conjugates for metal intoxication therapy

In a quest for better chelating therapy drugs for the treatment of intoxication by Fe, Al, or actinides, three new series of bisphosphonates conjugated with catechol were synthesized. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:251–257, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20013     

Synthesis and anticancer activities of porphyrin induced anticancer drugs

In view of the property of porphyrin's accumulation selectively in tumor,the ftorafur was modified by binding a porphyrin block to improve its tumor targeting and reduce its side effects.These novel porphyrin derivatives and metal compounds were synthesized under mild conditions with satisfactory yield,and the constructions of all these new compounds were characterized by UV,IR,MS, ~1H NMR spectra and elementary analysis.Their anticancer activities were evaluated by MTT assay;the results indicated that the anticancer activities of compounds 4a-c were twice as high as that of ftorafur.     

New flavonoid–porphyrin conjugates via Buchwald–Hartwig amination: synthesis and photophysical studies

New flavonoid–porphyrin conjugates were synthesized using the cross-coupling Buchwald–Hartwig amination for the coupling of flavonoid and porphyrin moieties. A unique di-substituted flavone–porphyrin conjugate was also synthesized under similar reaction conditions for the first time. All the conjugates were fully characterized by NMR spectroscopy. The photophysical properties namely fluorescence and singlet oxygen production were evaluated considering their use for photodynamic therapy applications.     

A molecular modeling study of complex formation and self-aggregation behavior of a porphyrin–β-cyclodextrin conjugate

This paper reports a molecular modeling study of complex formation and aggregation behavior of a supramolecular system comprising three different moieties forming two distinct molecules. One molecule is a phenol derivative of porphyrin conjugated to a macrocyclic oligosaccharide, β-cyclodextrin (β-CD), and the other is 1-adamantanol (ADM). The inclusion complex of the latter molecule with the porphyrin–β-cyclodextrin (β-CD) conjugate, and the dimeric aggregates of the conjugate both in the presence and in the absence of the guest are investigated through molecular mechanics and molecular dynamics methods in vacuo, since the systems are scarcely soluble in polar solvents. In this way, we can find the most likely geometry of the complexes or aggregates and characterize the competitive inclusion behavior of ADM and of a porphyrin phenol within the β-CD cavity in terms of the various energy contributions stabilizing the resulting aggregates and/or inclusion complexes.