Three New Chromone Derivatives Produced by Phomopsis sp. HNY29‐2B from Acanthus ilicifolius Linn.

Three new chromone derivatives, phomochromenones A‐C ( 1–3 ), and one known chaetocyclinone B ( 4 ) were obtained from the cultures of Phomopsis sp. HNY29‐2B isolated from the mangrove Acanthus ilicifolius Linn., which was collected from the South China Sea. Their structures were determined by the analysis of ¹D NMR and ²D NMR as well as mass spectroscopic data. The absolute configurations of 1 and 2 were assigned by quantum chemical calculations of the electronic circular dichroism (ECD ) spectra. Compound 3 is the third example of alkaloids possessing the unique chromeno [3,2‐c ] pyridine nucleus. In the bioactivity assay, compound 4 showed cytotoxicity against human prostate cancer cell lines (PC ‐3 and DU145 cells) with the IC₅₀ values of 8.13 and 3.59 µmol/L, respectively.     

Dendronized Anionic Gold Nanoparticles: Synthesis,Characterization, and Antiviral Activity

Anionic carbosilane dendrons decorated with sulfonate functions and one thiol moiety at the focal point have been used to synthesize water‐soluble gold nanoparticles (AuNPs) through the direct reaction of dendrons, gold precursor, and reducing agent in water, and also through a place‐exchange reaction. These nanoparticles have been characterized by NMR spectroscopy, TEM, thermogravimetric analysis, X‐ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, elemental analysis, and zeta‐potential measurements. The interacting ability of the anionic sulfonate functions was investigated by EPR spectroscopy with copper(II) as a probe. Different structures and conformations of the AuNPs modulate the availability of sulfonate and thiol groups for complexation by copper(II). Toxicity assays of AuNPs showed that those produced through direct reaction were less toxic than those obtained by ligand exchange. Inhibition of HIV‐1 infection was higher in the case of dendronized AuNPs than in dendrons.     

Nonionic Dendritic and Carbohydrate Based Amphiphiles: Self‐Assembly and Transport Behavior

Herein, a new series of non‐ionic dendritic and carbohydrate based amphiphiles is synthesized employing biocompatible starting materials and studied for supramolecular aggregate formation in aqueous solution. The dendritic amphiphiles 12 and 13 possessing poly(glycerol) [G2.0] as hydrophilic unit and C‐10 and C‐18 hydrophobic alkyl chains, respectively, exhibit low critical aggregation concentration (CAC) in the order of 10⁻⁵m and hydrodynamic diameters in the 8–10 nm range and supplemented by cryogenic transmission electron microscopy. Ultraviolet‐visible (UV‐Vis) and fluorescence spectroscopy suggests the effective solubilization of hydrophobic guests by the self‐assembled architectures, with the nanotransporters 12 and 13 possessing the highest encapsulation efficiency of 80.74 and 98.03% for curcumin. Efficient uptake of encapsulated curcumin in adenocarcinomic human alveolar basal epithelial (A549) cells is observed by confocal laser scanning microscopy. Amphiphiles 12 and 13 are non‐cytotoxic at the concentrations studied, however, curcumin encapsulated samples efficiently reduce the viability of A549 cells in vitro. Experimental studies indicate the ability of amphiphile 13 to encapsulate 1‐anilinonaphthalene‐8‐sulfonic acid (ANS) and curcumin with binding constant of 1.16 × 105⁵m ⁻¹ and 1.43 × 10⁶m ⁻¹, respectively. Overall, our findings demonstrate the potential of these dendritic amphiphiles for the development of prospective nanocarriers for the solubilization of hydrophobic drugs.     

Phospholipid lung surfactant and nanoparticle surface toxicity: Lessons from diesel soots and silicate dusts

Because of their small size, the specific surface areas of nanoparticulate materials (NP), described as particles having at least one dimension smaller than 100 nm, can be large compared with micrometer-sized respirable particles. This high specific surface area or nanostructural surface properties may affect NP toxicity in comparison with micrometer-sized respirable particles of the same overall composition. Respirable particles depositing on the deep lung surfaces of the respiratory bronchioles or alveoli will contact pulmonary surfactants in the surface hypophase. Diesel exhaust ultrafine particles and respirable silicate micrometer-sized insoluble particles can adsorb components of that surfactant onto the particle surfaces, conditioning the particles surfaces and affecting their in vitro expression of cytotoxicity or genotoxicity. Those effects can be particle surface composition-specific. Effects of particle surface conditioning by a primary component of phospholipid pulmonary surfactant, diacyl phosphatidyl choline, are reviewed for in vitro expression of genotoxicity by diesel exhaust particles and of cytotoxicity by respirable quartz and aluminosilicate kaolin clay particles. Those effects suggest methods and cautions for assaying and interpreting NP properties and biological activities.     

A ruthenium(II)-trithiacyclononane curcuminate complex: Synthesis,characterization, DNA-interaction,and cytotoxic activity

The coordination of ruthenium(II) complexes to anionic oxygen-based donors are very rare. This study describes a simple, one-pot method for obtaining [ruthenium(II)(trithiacyclononane)(curcumin)(S-DMSO)]Cl (1) in 37% yield. The structural characterization of complex 1 by elemental analysis, FT-IR, 1-D and 2-D NMR, ESI⁺-MS as well as UV–vis and fluorescence spectroscopies are presented. The DNA-melting temperature (T_m) assay shows that salmon sperm DNA (smDNA) in the presence of complex 1 has a higher melting temperature, with ΔT_m = 7.4 °C, while in the presence of curcumin the melting temperature remains unaltered. The in vitro cytotoxic activities of curcumin and complex 1 were investigated using the tumor human prostate cell line, PC-3, and the healthy cell line, PNT-2. Complex 1 is innocuous toward normal prostate epithelial cells and, whereas curcumin is toxic, with inhibition rates of ca. 35 and 65% at 50 and 80 μM, respectively. On the tumor cell line PC-3, complex 1 did not cause viability changes, whereas curcumin exhibited dose-dependent inhibition, with ca. 73% inhibition at the highest concentration tested, i.e. 80 μM. This study suggests that coordination with the trithiacyclononane ruthenium(II) scaffold stabilizes the photochemical properties of curcumin and strongly changes its biologic activity.     

三个单核钌配合物的合成、表征及抗肿瘤活性

对3种单核钌配合物[Ru（bpy）₂（paH）]PF₆（1）, [Ru（dmb）₂（paH）]PF₆（2）, [Ru（phen）₂（paH）]PF₆（3） （bpy=2,2''-联吡啶, dmb=4,4''-二甲基-2,2''-联吡啶, phen=菲咯啉, paH=2-吡啶甲酸）进行合成,并通过元素分析、红外、核磁和电喷雾质谱对其进行表征。此外,对配合物进行了光谱学和电化学测试,电化学实验表明1~3在0.7~1.0 V范围内均有1个氧化还原峰,说明钌中心发生了氧化还原反应。最后通过MTT法（MTT为3-（4, 5-二甲基噻唑-2）-2,5-二苯基四氮唑溴盐）对配合物进行了体外细胞毒性实验,结果表明：1~3对人乳腺癌细胞、胃癌细胞和肺癌细胞都表现出浓度依赖性,即随着配合物浓度的逐渐增大,细胞的存活率逐渐降低。值得注意的是2对乳腺癌细胞表现出非常明显的抑制作用（IC₅₀=2.85 μmol·L^-1）。     

Synthesis and Anticancer Properties of Rare Earth Substituted Tungstophosphoric Polyoxometalate Containing 5-Fluorouracil

Three novel rare earth substituted polyoxometalates containing 5‐fluorouracil, K₁₀C₄H₄FN₂O₂Pr(PW₁₁O₃₉)₂·24H₂O, K₁₀C₄H₄FN₂O₂Nd(PW₁₁O₃₉)₂·12H₂O and K₁₀C₄H₄FN₂O₂Sm(PW₁₁O₃₉)₂·12.5H₂O were synthesized and structurally characterized by elemental analysis, IR spectra, X‐ray powder diffraction and ¹⁸³W NMR. The results indicate that the compounds have Keggin structure of heteropolyanion and ring structure of 5‐fluorouracil. The cytotoxicity test of the compounds in human renal embryonic cell HEK293 and the activity inhibiting human cervical carcinoma cell Hela were studied by the methyl thiazolyl tetrazolium method with 5‐fluorouracil for the positive control group. The toxicity of the compounds are lower than that of 5‐fluorouracil. K₁₀C₄H₄FN₂O₂Pr(PW₁₁O₃₉)₂·24H₂O has no apparent toxicity in vitro and can inhibit Hela cells in vitro with significant difference compared with 5‐Fu.     

Small Noncytotoxic Carbon Nano‐Onions: First Covalent Functionalization with Biomolecules

Small carbon nano‐onions (CNOs, 6–8 shells) were prepared in high yield and functionalized with carboxylic groups by chemical oxidation. After functionalization these nanostructures were soluble in aqueous solutions. 3‐(4,5‐dimethylthiazol‐2‐yl)‐5‐(3‐carboxymethoxyphenyl)‐2‐(4‐sulfophenyl)‐2 tetrazolium (MTS) tests showed excellent cytocompatibility of all CNOs analyzed at 30 and 300 μg mL^?1, so these carbon nanostructures can be safely used for biological applications. The first covalent functionalization of oxidized CNOs (ox‐CNOs) with biomolecules, by using biotin–avidin interactions is reported here. Multilayers were prepared on a gold surface by layer‐by‐layer assembly and the process was monitored by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM). Covalent binding of molecules to the short amine‐terminated organosulfur monolayers was assessed by Fourier transform infrared spectroscopy using total attenuated reflactance mode (FT‐IR/HATR).     

Influence of structural features on the self‐assembly of short ionic oligopeptides

We investigated the self‐aggregation of 12 short ionic oligopeptides constituted by 4–7 amino acid residues to establish useful structure–property relationships that might be exploited in the biomedical field by using the concept of molecular Lego. We show that the critical aggregation concentration (CAC) of tetrapeptides decreases with increasing hydrophobicity of neutral residues. Additionally, the dependence of the CAC of isomeric oligopeptides on the distribution of amino acid residues confirms the high tendency to self‐organization of molecules with alternating ionic and neutral residues. Indeed, atomic force microscopy (AFM) images recorded on oligopeptide solutions above the CAC show the presence of either fibrillar or spherical aggregates depending on oligopeptide structure and concentration, steric hindrance, solution pH, and time. The potential of the investigated oligopeptides in tissue engineering applications is supported by their in vitro cytocompatibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 889–897, 2010