Protein Protection by Antioxidants: Development of a Convenient Assay and Structure‐Activity Relationships of Natural Polyphenols

In this work, a convenient test of antioxidant activity was developed, with BChE‐contaminated HSA as the target of AAPH‐induced oxidation and its esterase activity as the marker of protein integrity or degradation. The method is relatively simple, of low cost, and convenient to use. Its application to natural polyphenols showed that quercetin ( 1 ), verbascoside ( 2 ), chlorogenic acid ( 3 ), caffeic acid ( 4 ), 1,3,6,7‐tetrahydroxyxanthone ( 5 ), and mangiferin ( 6 ), are good antioxidants (IC₅₀<9 μM ). 1,5‐Dihydroxy‐3‐methoxyxanthone ( 7 ), flemichin D ( 8 ), and cordigone ( 9 ) showed modest activities (ca. 50 μM <IC₅₀<350 μM ), whereas danthrone ( 10 ) was inactive. Complementary experiments with two of the more active antioxidants, namely quercetin ( 1 ) and chlorogenic acid ( 3 ) showed that both antioxidants were better radical scavengers than chain‐breaking antioxidants. The relative adiabatic oxidation potential (ΔH_ox), the relative H‐bond dissociation energy (ΔH_abs), and the first oxidation potential measured by cyclic voltammetry were found to be related to the radical‐scavenging activity of these antioxidants.     

Structure–Function Relationships in Unsymmetrical Zinc Phthalocyanines for Dye‐Sensitized Solar Cells

Let it shine! The impact of the anchoring group on photovoltaic performance by a series of phthalocyanine sensitisers (see figure) has been demonstrated.

     

Influence of α- and γ- cyclodextrin lipophilic derivatives on curcumin-loaded SLN

Solid lipid nanoparticles (SLN) made of different triglycerides (TG) in the presence and in the absence of various modified α- and γ-cyclodextrins (CD) were prepared by the solvent injection technique. A new synthesis of lipophilic derivatives of γ- CD was developed in this work. Curcumin (CU), a natural polyphenol with antitumor, antioxidant and anti-inflammatory properties, was used as model drug. SLNs mean sizes were in the 250–800 nm range and afforded CU entrapment efficiency in the 12–85% range. The presence of CD derivatives with almost the same chain length of TG induced an improvement of nanoparticle characteristics decreasing mean size values and increasing CU entrapment efficiency. A significant reduction in CU photodegradation was noted only when the drug was vehicled in tristearin-SLN, which became less pronounced in the presence of CD-derivatives, determining a loss in photoprotection. The hydrolytic stability of curcumin was highly improved by drug loading in tristearin-SLN, and only slightly by loading it in tricaprin-SLN, and this seemed not to be influenced by the presence of CD derivatives. Skin uptake studies revealed an increase in CU skin accumulation when CU was loaded in SLN obtained with all CD derivatives, particularly with most lipophilic one.     

Inside Cover: A Spherical Molecule with a Carbon‐Free Ih‐C80 Topological Framework (Angew. Chem. Int. Ed. 27/2009)

Template‐controlled self‐assembly of discrete molecular pentaphosphaferrocene and CuCl units was used to form the first entirely carbon‐free molecule that has C₈₀ topology and encapsulates a carborane unit. In their Communication on page 5046 ff. , M. Scheer and co‐workers report the synthesis and characterization of this impressive supramolecular compound, which displays an electronic interaction between the carborane and the spherical host molecule. C blue, Fe olive, P pink, Cl green, C gray, B/C orange, H white.

     

Forces between mica surfaces, prepared in different ways, across aqueous and nonaqueous liquids confined to molecularly thin films

We have measured normal and lateral interactions across a range of different liquids between mica surfaces using a surface force balance (SFB). The mica surfaces were prepared either by melt cutting using Pt wire and standard procedures in our laboratories or by tearing sheets (that had not been exposed to Pt) off from a freshly cleaved sheet of mica. AFM micrographs revealed the substantial absence of Pt nanoparticles on the melt cut and torn-off mica surfaces. Normal-force versus surface-separation (D) profiles and shear force versus D measurements for purified water (no added salt), for concentrated aqueous NaCl solutions, and for cyclohexane revealed that in all cases the behavior of the highly confined liquids between melt-cut and between torn-off mica sheets was identical within experimental scatter. These results demonstrate directly that interactions measured between melt-cut mica surfaces as routinely prepared using established procedures in our laboratories and in other laboratories are free of the effect of any Pt contamination.     

Intramolecular [4+2] cycloaddition of furfurylsubstituted homoallylamines to allylhalides,acryloyl chloride and maleic anhydride

Acylation of 4‐(furyl‐2)‐4‐R‐aminobut‐1‐enes and 4‐R‐4‐furfurylaminobut‐1‐enes with maleic anhydride, acryloyl chloride or allylhalides provided 3‐aza‐10‐oxatricyclo[5.2.1.0^1,5]decenes. The tricycles are formed via an initial amide formation followed by a stereoselective exo‐IMDAF (Intramolecular Diels‐Alder of Furan). In case of competing cycloaddition (for compounds possessing two furan or two dienophilic moieties) the most substituted fivemembered cycle is preferably annulated. Refluxing of 4‐R‐4‐furfurylaminobut‐1‐enes in acetic anhydride led to exo‐3‐aza‐11‐oxatricyclo[6.2.1.0^1,6]undecenes with the pseudoequatorial substituent R‐4. Treatment of 3‐aza‐10‐oxatricyclo[5.2.1.0^1,5]decenes with PPA at 90?110°C promoted cyclic ether opening, aromatization and intramolecular cyclization reactions sequence to give the corresponding tetracyclic compounds — tetrahydroisoindolo[2,1‐a]quinolines and tetrahydroisoindolo[2,1‐b][2]benzazepines in good yields. Unusual products of ipso‐substitution in aromatic ring were obtained on cyclization of N‐p‐R‐substituted 2‐allyl‐4‐oxo‐3‐aza‐10‐oxatricyclo[5.2.1.0^1,5]dec‐8‐enes.     

Determination of perfluorinated compounds in mollusks by matrix solid-phase dispersion and liquid chromatography–tandem mass spectrometry

Perfluorinated compounds (PFCs) have been used for over 40 years in different commercial and industrial applications mainly as surfactants and surface protectors and have become an important class of marine emerging pollutants. This study presents the development and validation of a new analytical method to determine the simultaneous presence of eight PFCs in different kinds of mollusks using matrix solid-phase dispersion (MSPD) followed by liquid chromatography–tandem mass spectrometry (LC-MS/MS). Simplicity of the analytical procedure, low volume of solvent and quantity of sample required, low global price, and integration of extraction and clean-up into a single step, are the most important advantages of the developed methodology. Solvent, solid support (dispersing agent), clean-up sorbent, and their amounts were optimized by means of an experimental design. In the final method, 0.5 g of sample are dispersed with 0.2 g of diatomaceous earth and transferred into a polypropylene syringe containing 4 g of silica as clean-up sorbent. Then, analytes are eluted with 20 mL of acetonitrile. The extract is finally concentrated to a final volume of 0.5 mL in methanol, avoiding extract dryness in order to prevent evaporation losses and injected in the LC-MS/MS. The combination of this MSPD protocol with LC-MS/MS afforded detection limits from 0.05 to 0.3 ng g⁻¹. Also, a good linearity was established for the eight PFCs in the range from limit of quantification (LOQ) to 500 ng mL⁻¹ with R ² > 0.9917. The recovery of the method was studied with three types of spiked mollusk and was in the 64–126% range. Moreover, a mussel sample was spiked and aged for more than 1 month and analyzed by the developed method and a reference method, ion-pair extraction, for comparison, producing both methods statistically equal concentration values. The method was finally applied to the determination of PFCs in different kinds of mollusks revealing concentrations up to 8.3 ng g⁻¹ for perfluoroundecanoic acid.