N-(substituted phenylcarbamo-thioyl)benzamides and Fe3O4@C18 core@shell nanoparticles. The new benzamides were prepared by an efficient method, then their structure was confirmed by spectral studies and elemental analysis and they were further loaded on Fe3O4@C18 nanostructures. Both the obtained benzamides and the resulting hybrid nanosystems were tested for their efficiency against planktonic and adherent fungal cells, as well as for their in vitro biocompatibility, using mesenchymal cells. The antibiofilm activity of the obtained benzamides was dependent on the position and nature of substituents, demonstrating that structure modulation could be a very useful approach to enhance their antimicrobial properties. The hybrid nanosystems have shown an increased efficiency in preventing the development of Candida albicans  biofilms and moreover, they exhibited a good biocompatibility, suggesting that Fe3O4@C18core@shell nanoparticles could represent promising nanocarriers for antifungal substances, paving the way to the development of novel effective strategies with prophylactic and therapeutic value for fighting biofilm associated C. albicans infections.The continuously increasing global impact of fungal infections is requiring the rapid development of novel antifungal agents. Due to their multiple pharmacological activities, thiourea derivatives represent privileged candidates for shaping new drugs. We report here the preparation, physico-chemical characterization and bioevaluation of hybrid nanosystems based on new 2-((4-chlorophenoxy)methyl)- Candida genus  are among the most frequently reported microbial species involved in biofilm associated infections pyrimidine [S. aureus, B. subtilis, P. aeruginosa and E. coli strains better—as well as antifungal activity on Trichoderma viridae and Aspergillus niger—than the standard ciprofloxacin drug and miconazole, respectively [B. subtilis, S. aureus and E. coli bacterial strains and the pathogenic fungi A. fumigatus, Geotrichumcandidum and Candida albicans. Acylthiourea derivatives of carboxymethyl chitosan exhibited a higher antimicrobial activity especially against Gram-positive bacteria and significant antifungal activity, shown mainly by the chloroacetyl derivatives [Thiourea derivatives are a class of privileged compounds, exhibiting a wide range of biological activities, such as antibacterial , antifunrimidine  etc. Novectively . Acetyl,ivatives . On the ivatives ,25,26.1a–l) were synthesized by a series of reactions as shown in The target compounds (The infrared absorption (IR) bands were given as w—weak, m—medium, s—strong, vs—very strong.1H-NMR and 13C-NMR and the constants (J) values in Hertz.The structures of the new compounds were also determined from their nuclear magnetic resonance (NMR) spectra. The new thiourea derivatives were dissolved in DMSO-d6 (hexadeuteriodimethyl sulphoxide) and the chemical shifts values, expressed in parts per million (ppm) were referenced downfield to tetramethylsilane, for The chemical shifts for hydrogen and carbon atoms were established also by gradient-selected absolute value correlation (gCOSY), gradient-selected heteronuclear multiple bond correlation (gHMBC), gradient selected heteronuclear single-quantum correlation (gHSQC)–DNMR experiments.1H-NMR data are reported in the following order: chemical shifts, multiplicity, the coupling constants, number of protons and signal/atom attribution. The apparent resonance multiplicity is described as s (singlet), d (doublet), t (triplet), m (multiplet), dd (double doublet), dt (double triplet), td (triple doublet), ddd (doublet of double doublets) and br (broad) signal.The 13C-NMR data the order is the following: chemical shifts and signal/atom attribution (Cq-quaternary carbon).For the 3O4@C18 nanoparticles show that all diffraction peaks can be easily indexed to be a pure cubic structure by the characteristic peaks [2θ = 30.2° (220), 35.5°(311), 43.2° (400), 54.5° (422), 57.1° (511), 62.7° (440), which matches well with the reported value, indicating the formation of Fe3O4 phase.The XRD (X-Ray Diffraction) pattern of the fabricated Fe18 organic shell on the surface of fabricated core@shell nanostructures. Two sharp bands at 2915 and 2848 cm−1 were attributed to the asymmetric –CH2– stretching and the symmetric –CH2– stretching, respectively. The peak recorded at about 1701 cm−1 at IR spectrum of the fabricated core@shell nanostructures showed the C=O stretching vibration of C18.The IR analysis identified the CThe size of fabricated core@shell nanostructure not exceeding 15 nm and their spherical shape were confirmed by TEM (Transmission Electron Microscopy) analysis according to our previous published results .1h and 1i proved to slightly inhibit the development of C. albicans biofilms at 24 h, when they were pelliculised on the glass slide support. In exchange, when incorporated into nanoparticles, the majority of the tested compounds (excepting 1g and 1h) proved to prevent efficiently the biofilm development on the functionalized surfaces, as compared with the negative control, represented by the glass slide pelliculised only with nanoparticles  allowed the adherence and proliferation of the eukaryotic cells, in a similar manner to that observed on the microscopic slides control .C. albicans is the major human fungal pathogen causing a variety of clinical infections, ranging from superficial mucosal diseases to deep mycoses, being usually associated with biofilm development on medical devices [C. albicans. The fungal biofilms developed on different substrata, such as cellulose, poly-styrene, silicone, polyurethane and acrylate proved to exhibit multifactorial resistance mechanisms to many classes of antifungal agents [Candida biofilms to antifungal agents was first demonstrated in 1995 [C. albicans biofilms developed on polyvinyl chloride (PVC) discs than against planktonic cells and drug concentrations required to reduce metabolic activity by 50% were five to eight times higher for biofilms and 30–2000 times higher than the corresponding minimum inhibitory concentrations (MICs). devices . After al agents . Resista in 1995 . All cliN-(substituted phenylcarbamothioyl)benzamides, exhibiting antifungal activity.These findings are clearly demonstrating the necessity of finding new strategies for fighting fungal biofilm-associated infections. Two main research directions have been approached, i.e.,: (a) development of biomaterials with anti-adhesive properties using physico-chemicals methods and (b) incorporation in or coating current biomaterials with bioactive antifungal compounds . In the The chemical structures of the new compounds were characterized by their melting point, elemental analysis, infrared and NMR spectral studies. The spectral data and elemental analysis data of the new compounds were in agreement with the proposed structures. The obtained compounds proved to successfully inhibit the early fungal biofilms, quantified after 24 h. The less efficiency of the tested derivatives against the 48 h biofilms could be explained by the complex structure of these mature biofilms, consisting of a dense network of yeasts, hyphae and pseudohyphae, as demonstrated by previous in vitro studies using plastic surfaces and catheter samples . In contOur previous studies have demonstrated that magnetite nanoparticles could be used for the design of hybrid nanostructures that improve the antimicrobial activity of chemical substances and essential oils. Our results are demonstrating that the combination between nanoparticles and certain thiourea derivatives could act as efficient antibiofilm agents. However, to confirm the medical utility of these combinations, in vivo studies and clinical trials are further needed.metha-methyl and metha-methoxy, iodine, chlorine and nitro in different positions, proved the same antibiofilm efficiency when loaded into nanoparticles. The less active compounds were 1a, 1c, 1g and 1h, having as substituents ortho-methyl, ortho-methoxy, metha-bromide, 1, 6-di-bromide. Our results show that the substitution in metha position with methyl and methoxy groups, is favorable for the antibiofilm effect as compared with that in ortho for the same functional groups. The substitution with bromide, irrespective to the position or number of the substituent groups is not favorable for the occurrence of an antibiofilm effect.The derivatives, having as substituents The promising anti-adherence properties of the obtained nanosystems are enhanced by their increased in vitro biocompatibility, assessed on human mesenchymal cells.The obtained results are clearly demonstrating that the magnetic nanoparticles are improving the antifungal effect of the new thiourea derivatives, probably by modifying their functional groups and by increasing the volume surface ratio and thus the contact between the active compound and microbial target.2CO3 and then distilled and ammonium thiocyanate which was treated by heating at 100 °C before use.The chemicals for the synthesis of the new thioureides were purchased from Merck , and Sigma-Aldrich  companies and used as such without further purification except acetone which was dried over KMelting points were determined with an Electrothermal 9100  capillary melting point apparatus in open capillary tubes and are uncorrected.C, H, N and S analysis were carried out on a Perkin Elmer CHNS/O Analyzer Series II 2400 elemental analyzer .The room temperature attenuated total reflection Fourier transform infrared (FT-IR ATR) spectra of the all synthesized compounds were registered using a Bruker Vertex 70 spectrophotometer .1H and 100 MHz for 13C.All NMR spectra were recorded on a Varian Unity Inova 400 instrument  operating at 400 MHz for 2) and 2-(4-chlorophenoxy-methyl)benzoyl chloride (3) derivatives were prepared in good yields according to the previous article [The 2-(4-chlorophenoxymethyl)benzoic acid benzoyl chloride (3) (0.01 mol) in acetone (15 mL) was added to a solution of ammonium thiocyanate (0.01 mol) in acetone (5mL) to afford arylisothiocyanate (4) in situ. The reaction mixture was heated under reflux for 1 h and then cooled at the room temperature. A solution of primary amine (0.01 mol) in acetone (2 mL) was added to the mixture and heated under reflux for 1 h. The acylthioureas were precipitated after the cooled reaction mixture was poured into 500 mL water. The solid product was purified by recrystallization from isopropanol with active carbon.The compounds 2-((4-Chlorophenoxy)methyl)-N-(2-methylphenylcarbamothioyl)benzamide (1a). Yield 68%; melting temperature (mp) 147.4–149 °C; 1H-NMR (DMSO-d6): 12.11 ; 11.88 ; 7.62 ; 7.59 ; 7.57 ; 7.49 ; 7.47 ; 7.33–7.18 ; 7.31 ; 7.01 ; 5.31 ; 2.13 ; 13C-NMR (DMSO-d6): 179.76 (C-16); 170.08 (C-1); 156.97 (C-9); 136.68 (Cq); 135.04 (Cq); 133.44 (Cq); 133.20 (Cq); 130.90; 130.28; 129.17 ; 128.57; 128.49; 127.90; 126.91; 126.42; 125.97; 124.62 (C-12); 116.34 ; 67.81 (C-8); 17.33 (C-18’). FT-IR : 3163m; 3057w; 2864w; 1682s; 1594w; 1509vs; 1488vs; 1460m; 1383w; 1329w; 1238s; 1195w; 1168m; 1150m; 1089w; 1029w; 1005m; 849w; 767m; 676w; 655m. Anal. Calcd for C22H19ClN2O2S (410.91): C, 64.31; H, 4.66; Cl, 8.63; N, 6.82; S, 7.8%; Found: C, 64.61; H, 4.76; Cl, 8.71; N, 6.80; S, 7.84%.2-((4-Chlorophenoxy)methyl)-N-(3-methylphenylcarbamothioyl)benzamide (1b). Yield 68%; mp 126.9–128.6 °C; 1H-NMR (DMSO-d6): 12.37 ; 11.82 ; 7.62 ; 7.59 ; 7.57 ; 7.48 ; 7.43 ; 7.32 ; 7.29 ; 7.08 ; 7.31 ; 7.01 ; 5.31 ; 2.33 . 13C-NMR (DMSO-d6): 178.75 (C-16); 170.04 (C-1); 156.96 (C-9); 137.99 (Cq); 137.63 (Cq); 135.15 (Cq); 133.28 (Cq); 130.96; 129.16 ; 128.46; 128.36; 128.34; 127.83; 126.87; 124.54 (C-12); 124.48; 121.26; 116.36 ; 67.75 (C-8); 20.80 (C-19’). FT-IR : 3158m; 3024m; 2884w; 1680s; 1596m; 1528vs; 1487s; 1379m; 1325m; 1275m; 1240s; 1174m; 1151s; 1083m; 1003m; 825m; 789w; 773w; 747m; 720m; 692w; 668w; 643w. Anal. Calcd for C22H19ClN2O2S (410.91): C, 64.31; H, 4.66; Cl, 8.63; N, 6.82; S, 7.8%; Found: C, 64.09; H, 4.61; Cl, 8.72; N, 6.87; S, 7.76%.2-((4-Chlorophenoxy)methyl)-N-(2-methoxyphenylcarbamothioyl)benzamide (1c). Yield 64%; mp 128.4–130.6 °C; 1H-NMR (DMSO-d6): 12.74 ; 11.82 ; 8.51 ; 7.65 ; 7.60 ; 7.59 ; 7.49 ; 7.29 ; 7.23 ; 7.12 ; 7.02 ; 7.01 ; 5.34 ; 3.96 . 13C-NMR (DMSO-d6): 177.64 (C-16); 169.99 (C-1); 156.90 (C-9); 150.42 (C-18); 135.03 (Cq); 133.34 (Cq); 130.92; 129.07 ; 128.54; 128.48; 127.87; 126.67 (C-17); 126.48; 124.58 (C-12); 123.03; 119.61 (C-19); 116.38 ; 111.18 (C-19); 67.86 (C-8); 55.84 (C-18’). FT-IR : 3288w; 3002w; 2937w;2837w; 1667w; 1601s; 1554vs;1529vs; 1486s; 1463m; 1356s; 1325m; 1287m; 1241vs; 1222m; 1181m; 1151m; 1051w; 1027s; 818m; 794w; 735m; 692w; 665w. Anal. Calcd for C22H19ClN2O3S (426.91): C, 61.90; H, 4.49; Cl, 8.30; N, 6.56; S, 7.51%; Found: C, 61.69; H, 4.36; Cl, 8.21; N, 6.58; S, 7.54%.2-((4-Chlorophenoxy)methyl)-N-(3-methoxyphenylcarbamothioyl)benzamide (1d). Yield 67%; mp 133–135.2 °C; 1H-NMR (DMSO-d6): 12.42 ; 11.83 ; 7.63 ; 7.59 ; 7.57 ; 7.48 ; 7.34 ; 7.31 ; 7.31 ; 7.11 ; 7.01 ; 6.84 ; 5.31 ; 3.77 . 13C-NMR (DMSO-d6): 178.62 (C-16); 169.97 (C-1); 159.21 (C-19); 156.94 (C-9); 138.81 (Cq); 135.18 (Cq); 133.20 (Cq); 131.00; 129.35; 129.15 ; 128.50; 128.33; 127.81; 124.61 (C-12); 116.39 ; 116.19; 111.84; 109.52; 67.71 (C-8); 55.12 (C-19’). FT-IR : 3293w; 3056w; 2998w; 2955w; 2916w; 2832w; 1671m; 1597m; 1570m; 1528vs; 1489s; 1469m; 1380m; 1355m; 1330m; 1277s; 1239vs; 1154s; 1121m; 1102m; 1032m; 1005w; 813m; 779w; 756w; 689m; 647w. Anal. Calcd for C22H19ClN2O3S (426.91): C, 61.90; H, 4.49; Cl, 8.30; N, 6.56; S, 7.51%; Found: C, 62.07; H, 4.56; Cl, 8.41; N, 6.51; S, 7.62%.2-((4-Chlorophenoxy)methyl)-N-(2-chlorophenylcarbamothioyl)benzamide (1e). Yield 76%; mp 124.3–125.7 °C; 1H-NMR (DMSO-d6): 12.47 ; 12.06 ; 7.96 ; 7.65 ; 7.60–7.55 ; 7.49 ; 7.40 ; 7.32 ; 7.30 ; 7.01 ; 5.31 . 13C-NMR (DMSO-d6): 179.89 (C-16); 170.21 (C-1); 156.91 (C-9); 135.13 (Cq); 133.19 (Cq); 131.03; 129.37; 129.12 ; 128.58; 128.56; 128.01; 127.92; 127.73; 127.08; 124.60 (C-12); 116.35 ; 67.80 (C-8). FT-IR : 3247m; 3031w; 2923w; 1675m; 1582m; 1527vs; 1491vs; 1444m; 1386w; 1325m; 1283m; 1243vs; 1159s; 1095w; 1034m; 815m; 796w; 747m; 728w; 685m; 662w. Anal. Calcd for C21H16Cl2N2O2S (431.33): C, 58.48; H, 3.74; Cl, 16.44; N, 6.49; S, 7.43%; Found: C, 58.27; H, 3.61; Cl, 16.51; N, 6.51; S, 7.38%.2-((4-Chlorophenoxy)methyl)-N-(3-chlorophenylcarbamothioyl)benzamide (1f). Yield 66%; mp 118.1–119.8 °C; 1H-NMR (DMSO-d6): 12.40 ; 11.92 ; 7.81 ; 7.64 ; 7.59 ; 7.57 ; 7.48 ; 7.46 ; 7.43 ; 7.33 ; 7.31 ; 7.01; 5.31 . 13C-NMR (DMSO-d6): 179.17 (C-16); 169.87 (C-1); 156.93 (C-9); 139.20 (Cq); 135.21 (Cq); 133.15 (Cq); 132.56 (Cq); 131.04 (Cq); 130.16; 129.15 ; 128.49; 128.35; 127.83; 126.04; 124.62 (C-12); 123.98; 123.07; 116.35 ; 67.69 (C-8). FT-IR : 3222m; 3105m; 3062m; 3034m; 1666m; 1585m; 1525vs; 1491vs; 1479vs; 1437s; 1413m; 1323m; 1292m; 1237vs; 1153s; 1092m; 1051m; 1025m; 949w; 872w; 814m; 751m; 722m; 704m; 679m; 658m. Anal. Calcd for C21H16Cl2N2O2S (431.33): C, 58.48; H, 3.74; Cl, 16.44; N, 6.49; S, 7.43%; Found: C, 58.31; H, 3.65; Cl, 16.56; N, 6.45; S, 7.47%.2-((4-Chlorophenoxy)methyl)-N-(3-bromophenylcarbamothioyl)benzamide (1g). Yield 73%; mp 126–127.7 °C; 1H-NMR (DMSO-d6): 12.39 ; 11.92 ; 7.93 ; 7.62 ; 7.59 ; 7.57 ;7.53–7.44 ; 7.37 ; 7.31 ; 7.01 ; 5.31 . 13C-NMR (DMSO-d6): 179.19 (C-16); 169.87 (C-1); 156.94 (C-9); 139.33 (Cq); 135.22 (Cq); 133.16 (Cq); 131.04; 130.43; 129.14 ; 128.93; 128.48; 128.35; 127.83; 126.82; 124.65 (C-12); 123.48; 120.84 (C-19); 116.37 ; 67.72 (C-8). FT-IR : 3220m; 3106w; 3058m; 3035m; 1666m; 1582m; 1526vs; 1491vs; 1477s; 1437m; 1410m; 1323m; 1292m; 1238vs; 1162s; 1091m; 1028s; 1005m; 816m; 772m; 706m; 678m; 658w. Anal. Calcd for C21H16BrClN2O2S (475.78): C, 53.01; H, 3.39; Br, 16.79; Cl, 7.45; N, 5.89; S, 6.74%; Found: C, 53.37; H, 3.25; Br, 16.83; Cl, 7.36; N, 6.45; S, 6.76%.2-((4-Chlorophenoxy)methyl)-N-benzamide (1h). Yield 43%; mp 200.4–202.2 °C; 1H-NMR (DMSO-d6): 12.12 ; 11.93 ; 7.72 ; 7.64 ; 7.59 ; 7.57 ; 7.48 ; 7.31 ; 7.21 ; 7.01 ; 5.29 . 13C-NMR (DMSO-d6): 180.52 (C-16); 169.79 (C-1); 156.92 (C-9); 138.69 (Cq); 136.69 (Cq); 134.97 (Cq); 133.33 (Cq); 132.07 ; 131.08; 130.42; 129.12 ; 128.56; 128.07; 124.52 (C-12); 123.97 ; 116.44 ; 67.65 (C-8). FT-IR : 3155s; 3003m; 2935w; 2861w; 1686s; 1504vs; 1488vs; 1459s; 1430m; 1388m; 1346m; 1260m; 1237s; 1171s; 1153m; 1104m; 1078m; 1050w; 1029m; 1005m; 825m; 772m; 746m; 728m; 675w; 654m. Anal. Calcd for C21H15Br2ClN2O2S (554.68): C, 45.47; H, 2.73; Br, 28.81; Cl, 6.39; N, 5.05; S, 5.78%; Found: C, 45.29; H, 2.89; Br, 28.98; Cl, 6.31; N, 6.11; S, 5.66%.2-((4-Chlorophenoxy)methyl)-N-(2-iodophenylcarbamothioyl)benzamide (1i). Yield 78%; mp 152.7–154.2 °C; 1H-NMR (DMSO-d6): 12.22 ; 12.03 ; 7.92 ; 7.65 ; 7.62–7.55 ; 7.50 ; 7.44 ; 7.32 ; 7.08 ; 7.02 ; 5.32 . 13C-NMR (DMSO-d6): 180.24 (C-16); 170.08 (C-1); 156.93 (C-9); 140.05 (Cq); 138.79 (Cq); 135.10 (Cq); 133.23 (Cq); 131.08; 129.19 ; 128.78; 128.69; 128.67; 128.39; 127.94; 124.59 (C-12); 116.44 ; 129.86; 96.96 (C-18); 67.68 (C-8). FT-IR : 3220m; 3026w; 1674m; 1571w; 1525vs; 1490vs;1434m; 1389m; 1320m; 1278m; 1242vs; 1162s; 1093w; 1037m; 1016w; 815m; 745m; 712m; 683m; 662w. Anal. Calcd for C21H16ClIN2O2S (522.78): C, 48.25; H, 3.08; Cl, 6.78; I 24.27; N, 5.36; S, 6.13%; Found: C, 48.49; H, 2.96; Cl, 6.61; I, 24.39; N, 5.29; S, 6.05%.2-((4-Chlorophenoxy)methyl)-N-(4-iodophenylcarbamothioyl)benzamide (1j). Yield 53%; mp 154.3–156.2 °C; 1H-NMR (DMSO-d6): 12.37 ; 11.88 ; 7.75 ; 7.62 ; 7.59 ; 7.57 ; 7.47 ; 7.43 ; 7.31 ; 7.00 ; 5.31 . 13C-NMR (DMSO-d6): 178.85 (C-16); 169.86 (C-1); 156.92 (C-9); 137.62 (Cq); 137.22 ; 135.20 (Cq); 133.14 (Cq); 131.03; 129.15 ; 128.50; 128.32; 127.80; 126.34 ; 124.62 (C-12); 116.38 ; 91.00 (C-20); 67.68 (C-8). FT-IR : 3347s; 3156w; 3326m; 2907w; 1676m; 1595m; 1581m; 1547m; 1511s; 1486vs; 1443s; 1396m; 1330m; 1287m; 1239s; 1148s; 1030m; 1001m; 943w; 855w; 817m; 755m; 751m; 738m; 699w; 684w; 650m. Anal. Calcd for C21H16ClIN2O2S (522.78): C, 48.25; H, 3.08; Cl, 6.78; I 24.27; N, 5.36; S, 6.13%; Found: C, 48.09; H, 3.17; Cl, 6.89; I, 24.36; N, 5.34; S, 6.19%.2-((4-Chlorophenoxy)methyl)-N-(3-nitrophenylcarbamothioyl)benzamide (1k). Yield 59%; mp 165.6–167.4 °C; 1H-NMR (DMSO-d6): 12.53 ; 12.03 ; 8.66 ; 8.12 ; 7.94 ; 7.69 ; 7.65 ; 7.60 ; 7.59 ; 7.49 ; 7.30 ; 7.02 ; 5.32 . 13C-NMR (DMSO-d6): 179.54 (C-16); 169.80 (C-1); 156.94 (C-9); 147.41 (C-19); 139.00 (Cq); 135.27 (Cq); 133.14 (Cq); 131.10; 131.00; 129.86; 129.15 ; 128.51; 128.37; 127.85; 124.67 (C-12); 120.78; 118.94; 116.37 ; 67.71 (C-8). FT-IR : 3164m; 3083w; 2929w; 1685m; 1584vs; 1490s;1386w; 1344m; 1313w; 1278m; 1246m; 1230m; 1174m; 1151m; 1091w; 1070w; 1023m; 1003w;819m; 767w; 740m; 698w; 678w. Anal. Calcd for C21H16ClN3O4S (441.88): C, 57.08; H, 3.65; Cl, 8.02; N, 9.51; S, 7.26%; Found: C, 57.32; H, 3.57; Cl, 7.89; N, 9.56; S, 7.28%.2-((4-Chlorophenoxy)methyl)-N-(4-nitrophenylcarbamothioyl)benzamide (1l). Yield 68%; mp 173.5–175.2 °C; 1H-NMR (DMSO-d6): 12.69 ; 12.05 ; 8.27 ; 8.00 ; 7.65 ; 7.60 ; 7.59 ; 7.49 ; 7.30 ; 7.01 ; 5.32 . 13C-NMR (DMSO-d6): 178.96 (C-16); 169.81 (C-1); 156.90 (C-9); 144.23 (C-20); 143.78 (C-17); 135.31 (Cq); 133.00 (Cq); 131.15; 129.16 ; 128.56; 128.35; 127.82; 124.18 ; 123.89 ; 124.61 (C-12); 116.35 ; 67.63 (C-8). FT-IR : 3352m; 3078w; 2974m; 1678m; 1566m; 1513s; 1490vs; 1445m; 1332m; 1299s; 1262m; 1242vs; 1145s; 1111m; 1029m; 960w; 863m; 846m; 820w; 781w; 743m; 699w; 680w; 652m. Anal. Calcd for C21H16ClN3O4S (441.88): C, 57.08; H, 3.65; Cl, 8.02; N, 9.51; S, 7.26%; Found: C, 56.82; H, 3.77; Cl, 8.14; N, 9.59; S, 7.26%.3O4@C18 nanostructure was prepared and characterized in the same manner to our previously published papers that report the successful fabrication of Fe3O4@C14 and Fe3O4@C18 [18) was dispersed in 200 mL volume of distilled-deionized water, corresponding to a 0.50% (v/w) solution, under vigorous stirring at 60 °C. Five mL solution consisting of 25% NH3 was added to C18 dispersion. Fe2+:Fe3+ (1:2 molar ratio) were dropped under permanent stirring in aqueous solution of NH3, leading to the formation of a black precipitate. The product was repeatedly washed with methanol and separated with a strong NdFeB permanent magnet.Core@shell—Fee3O4@C18 ,35. Brie3O4@C18 nanostructure was confirmed by XRD, TEM and FT-IR.The successful fabrication of FeX-ray diffraction analysis was performed on a XRD 6000 diffractometer  at room temperature. In all the cases, Cu Kα radiation from a Cu X-ray tube (run at 15 mA and 30 kV) was used. The samples were scanned in the Bragg angle 2θ range of 10–80°.TEM images were obtained on finely powdered samples using a Tecnai™ G2 F30 S-TWIN high-resolution transmission electron microscope from FEI Company . The microscope was operated in transmission mode at 300 kV with TEM point resolution of 2 Å and line resolution of 1 Å. The fine hybrid nanostructure was dispersed into pure ethanol and ultrasonicated for 15 min. After that, diluted sample was put onto a holey carbon-coated copper grid and left to dry before TEM analysis.−1 with strong apodization, in the frequency range of 4000–650 cm−1 by co-adding 32 scans. All spectra were ratioed against a background of an air spectrum.A Nicolet 6700 FT-IR spectrometer , connected to the OMNIC operating system software  was used to obtain FT-IR spectra of hybrid materials. The samples were placed in contact with attenuated total reflectance (ATR) on a multibounce plate of ZnSe crystal at controlled ambient temperature (25 °C). FT-IR spectra were collected at a resolution of 4 cm1a–l) was solubilized in 1 mL of chloroform together with 135 mg Fe3O4@C18 and grounding until complete evaporation of chloroform. This step is repeated by three times for uniform distribution of the 1a–l on the surface of spherical nanostructure. The fabrication was performed by coating the coverslips with nanofluid represented by suspended core@shell@adsorption-shell in chloroform (0.33% w/v) according to our published papers [The adsorption-shell represented by 15 mg of  coated with the chemical compound, using as negative control the glass slide as well and respectively; (ii) magnetic nanoparticles loaded with the tested substances, using as negative control the glass slide covered with nanoparticles. Plastic wells were filled with 2 mL liquid medium, inoculated with 300 μL 0.5 McFarland fungal suspensions and incubated for 24 h at 37 °C. After 24 h, the culture medium was removed, the slides were washed three times in phosphate buffered saline (PBS) in order to remove the non-adherent strains and fresh glucose broth was added, the same procedure as mentioned above being repeated after 48 h incubation period. For each 24 h, viable cell counts have been achieved for both working variants in order to assess the biofilm forming ability of the two strains. To this purpose, the adhered cells have been removed from the slides by vortexing and brief sonication and serial dilutions ranging from 10−1 to 10−16 of the obtained inocula have been spotted on Muller Hinton agar, incubated for 24 h at 37 °C and assessed for viable cell counts.The microbial adherence ability was investigated in six multiwell plates, in which there have been placed 1 cm3 pieces) and treated with 2 mg/mL collagenase II for 3–4 h at 37 °C. Cell suspension was centrifuged, washed and resuspended in α-minimal essential medium  supplemented with 10% fetal bovine serum  and 10 ng/mL basic fibroblast growth factor (bFGF) . The cells were plated at a density of 1 × 104 cells/cm2 and cultured at 37 °C in a humidified atmosphere containing 5% CO2. The medium was changed every 3 days and passaged by trypsinization when the cells reached 70–80% confluence. Cells at the passage 14 of were used in our experiments. 2 × 105 cells were seeded on the functionalized slides distributed in 6 wells plate. 24 h later, the cells were fixed in ethanol 70% and stained with 50 µg/mL propidium iodide. The morphology of lived or stained cells were observed using Observer.D1 inverted microscope .Human umbilical cords were obtained under sterile conditions after birth from full-term infants, with the consent of the parents. The umbilical cord blood vessels (two arteries and one vein) were removed and the remaining tissue was diced into small fragments (1 mmN-(substituted phenylcarbamo-thioyl)benzamide by an efficient method. The structure of the prepared compounds was determined by spectral studies and elemental analysis. The antibiofilm effect of the obtained compounds was dependent on the position and nature of the substituents, demonstrating that structural modulation could be very useful to enhance the antimicrobial properties of thiourea analogs but also their interaction with potential carriers. The combinations of the tested compounds with fabricated Fe3O4@C18 resulted in increased efficiency in preventing the in vitro development of C. albicans biofilms, suggesting that the obtained hybrid nanosystems could represent an effective, biocompatible strategy with prophylactic and therapeutic value in fighting biofilm associated C. albicans infections.We have synthesized new 2-((4-chlorophenoxy)methyl)-


Pseudolysimachion rotundum var. subintegrum has been used as traditional medicine to treat inflammatory diseases. In this study, we assessed whether picroside II has inhibitory effects on airway inflammation in a mouse model of house dust mite (HDM)-induced asthma. In the HDM-induced asthmatic model, picroside II significantly reduced inflammatory cell counts in the bronchoalveolar lavage fluid (BALF), the levels of total immunoglobulin (Ig) E and HDM-specific IgE and IgG1 in serum, airway inflammation, and mucus hypersecretion in the lung tissues. ELISA analysis showed that picroside II down-regulated the levels of Th2-related cytokines  and asthma-related mediators, but it up-regulated Th1-related cytokine, IFNγ in BALF. Picroside II also inhibited the expression of Th2 type cytokine genes and the transcription factor GATA3 in the lung tissues of HDM-induced mice. Finally, we demonstrated that picroside II significantly decreased the expression of GATA3 and Th2 cytokines in developing Th2 cells, consistent with in vivo results. Taken together, these results indicate that picroside II has protective effects on allergic asthma by reducing GATA3 expression and Th2 cytokine bias.Picroside II isolated from  Allergic asthma is a chronic inflammatory disease characterized by infiltration of the airway wall with eosinophils and CD4+ T helper type 2 (Th2) cells, reversible airway obstruction, airway hyper-responsiveness (AHR), mucus hypersecretion and airway remodeling , 2. The Exposure to allergens causes differentiation of CD4+ T cells into effector T cells, Th1, Th2 and Th17 cells, which produce lineage-specific cytokines IFNγ, IL-4 and IL-17, respectively , 10. ThePseudolysimachion rotundum var. subintegrum that has been used as traditional medicine to treat inflammatory diseases ‒ ; [α]D20–158.7° ; 1H-NMR  δ2.47 , 2.58 , 3.03 , 3.07 , 3.14 , 3.18 , 3.44 , 3.72 , 3.67 , 3.72 , 3.93 , 3.82 (3'-OCH3), 4.63 , 4.97 , 5.06 , 5.11 , 6.42 , 6.85 , 7.46 , 7.52 ; 13C NMR (100 MHz) δ35.2 (C-5), 41.8 (C-9), 55.7 (3'-OCH3), 58.2 (C-7), 58.5 (C-10), 61.4 (Glc-6''), 65.9 (C-8), 70.3 (Glc-4''), 73.5 (Glc-2''), 76.5 (Glc-3''), 77.5 (Glc-5''), 79.4 (C-6), 93.0 (C-1), 97.9 (Glc-1''), 101.9 (C-4), 112.7 (C-2'), 115.3 (C-5'), 119.9 (C-1'), 123.9 (C-6'), 141.1 (C-3), 147.5 (C-3'), 152.1 (C-4'), 165.6 (C-7').(A) Spectra 1. (TIF)Click here for additional data file.S2 Fig2 was used as the desolvation gas. The desolvation temperature was set to 350°C at a flow rate of 500 L/h and source temperature of 100°C. The capillary and cone voltages were set to 2300 and 35 V, respectively. The Q-TOF premierTM was operated in V mode with 9000 mass resolving power. The data were collected for each test sample from 100 to 1500 Da with a 0.25 s scan time and a 0.01 s interscan delay over a 15 min analysis time. Leucine-enkephalin was used as the reference compound (m/z 554.2615 in the negative mode) and an infusion flow rate of 1 μl/min.(A) UPLC-PDA chromatogram of isolated picroside II. The ethanol extracts and subfractions were analyzed by UPLC PDA QTOF-MS. Chromatographic separations were performed on a 2.1 × 100 mm, 1.7 μm ACQUITY BEH C18 chromatography column. The column temperature was maintained at 35°C, and the mobile phases A and B were water with 0.1% formic acid and acetonitrile with 0.1% formic acid, respectively. The gradient duration program was: 0–1 min, 10% B; 1–10.5 min, 10–23% B; 10.5–12.0 min, 23–98% B; wash to 15.0 min with 98% B; and a 1.5 min recycle time. The flow rate was 0.4 mL/min. (B) UPLC-QTOF-MS and HREIMS data of picroside II. The mass spectrometer was operated in positive ion mode. N(TIF)Click here for additional data file.


R)-methoxycholest-5,24-dien-3β-ol (1), two new ceramides, -2-(tetradecanoylamino)-4,8-octadecadien-l,3-diol (6) and -2-(tetradecanoylamino)-4,8-octadecadien-l,3,2′-triol (7), together with three known sterols (2–4), a lactone (5) and two ceramides , were isolated from the marine bryozoan Cryptosula pallasiana, collected at Huang Island of China. The structures of the new compounds were elucidated by extensive spectroscopic analyses, chemical methods and quantum electronic circular dichroism (ECD) calculations. Among the isolated compounds, sterol 1 possessed a rare side chain with a methoxy group at C-23, and a double bond between C-24 and C-25. Ceramides 6 and 7 possessed 14 carbons in their long-chain fatty acid base (FAB), which were different from the normal ceramides with 16 carbons in the FAB. Moreover, compounds 5 and 8 were isolated for the first time from marine bryozoans. Compounds 1–9 were evaluated for their cytotoxicity against human tumor cell lines HL-60, Hep-G2 and SGC-7901. The results showed that lactone 5 appears to have strong cytotoxicity against the test tumor cell lines, with IC50 values from 4.12 μM to 7.32 μM, and sterol 1 displayed moderate cytotoxicity with IC50 values between 12.34 μM and 18.37 μM, while ceramides 6–9 showed weak cytotoxicity with IC50 ranging from 21.13 μM to 58.15 μM.A new sterol, (23 Cryptosula pallasiana is an encrusting colonial marine bryozoan, belonging to the class Gymnolaemata, order Cheilostomata and family Cryptosulidae. In our previous investigation on the bioactive compounds from this marine bryozoan, 16 alkaloids, 13 sterols, three aromatic compounds and two glycerol derivatives have been identified + . The 1H-NMR spectrum of 1 showed two tertiary methyl resonance signals at δH 0.73, s (H3-18) and 1.00, s (H3-19), three secondary methyl groups at δH 0.95, d, J = 5.9 Hz (H3-21), δH 1.67, d, J = 1.0 Hz (H3-26) and 1.74, d, J = 1.1 Hz (H3-27), one methoxy group at δH 3.21 s (OMe-23), two oxymethine protons at δH 3.52, m, (H-3) and 3.94, dt, J = 9.3, 3.1 Hz (H-23), and two tri-substituted olefinic protons at δH 5.35, t, J = 2.5 Hz (H-6) and 5.03, td, J = 9.0, 2.6, 1.3 Hz (H-24). The 13C-NMR spectrum showed 28 carbon resonances, which were assigned by distortionless enhancement by polarization transfer (DEPT) and heteronuclear single quantum coherence (HSQC) spectra to one methoxy carbon at δC 55.7 (OMe-23), five methyl , nine methylene sp3 , seven methine sp3  including two hydroxymethines C-3 (δC 71.8) and C-23 (δC 74.8), two quaternary sp3 carbons (C-10 and C-13), two methine sp2 carbons C-6 (δC 121.7) and C-24 (δC 127.0), and two quaternary sp2 carbons C-5 (δC 140.7) and C-25 (δC 134.5). These data suggested that 1 possessed a 3-hydroxy ∆5-steroid nucleus with a methoxy group and double bond in its side chain. Further structural information for compound 1 was obtained by 2D NMR analysis including 1H-1H correlation spectroscopy (COSY) and heteronuclear multiple bond correlation (HMBC) spectra  spectrum and quantum electronic circular dichroism (ECD) calculations. The 1H-NMR assignment of α and β protons for compound 1  + , which, together with the pseudomolecular ion peak at m/z 506 [M − H]− in the (‒)-ESIMS spectrum, enabled the determination of the molecular formula for 6 as C32H61NO3. A careful analysis of the 1H- and 13C-NMR spectra of 6 (C 174.0 (C-1′), δH 6.25, d, J = 7.5 Hz (NH), a nitrogen- or oxygen-bearing methine δC 54.5 (C-2), δH 3.95, dd, J = 11.3, 3.5 Hz (H-2), an oxymethylene sp3 δC 62.5 (C-1), δH 3.70, dd, J = 11.3, 3.3 Hz and 3.90, m (H2-1), an oxymethine sp3 δC 74.7 (C-3), δH 4.32, m (H-3), and four methine sp2 δC 129.2 (C-4), δH 5.54, dd, J = 15.4, 6.4 Hz (H-4); δC 133.6 (C-5), δH 5.78, dt, J = 15.4, 6.6 Hz (H-5); δC 131.4 (C-8), δH 5.42, dt, J = 15.2, 6.3 Hz (H-8) and δC 129.0 (C-9), δH 5.37, dt, J = 15.2, 6.4 Hz (H-9), which together with a series of alkyl proton signals , indicated an existence of a sphinga-4,8-diene skeleton for 6 +  and the 1H- and 13C-NMR spectra , C-2′ (δC 72.4) and C-3′ (δC 34.8) in its FAB. HMBC correlations of H-2′ (δH 4.12) to C-1′ and C-3′ confirmed that the hydroxyl group was on C-2′ -ESIMS spectrum (m/z 258 [M]+ of (R)-methyl 2-hydroxytetradecanoate obtained from methanolysis of 7. Comparisons of the optical rotation of 7 -2′-hydroxy-C16-ceramide ([α]D +5.2°) and its 2′S-isomer ([α]D −16.1°), suggested that 7 and -2′-hydroxy-C16-ceramide have the same absolute configurations for core chiral centers C-2, C-3 and C-2′ +, 415 [M + H]+, 385, 349, 318, 274, 256; (+)-HRESIMS m/z: 437.3395 [M + Na]+ .White amorphous powder, c 0.10, CHCl3); 1H- and 13C-NMR data see m/z: 530 [M + Na]+, 437, 330, 302, 274, 262, 256, 228, 219; (‒)-ESIMS m/z: 552 [M + COOH]−, 542 [M + Cl]−, 506 [M − H]−, 447, 394, 341, 283, 255, 218, 186, 143, 126; (+)-HRESIMS m/z: 530.4545 [M + Na]+ .White amorphous powder, c 0.10, CHCl3); 1H- and 13C-NMR data see m/z: 546 [M + Na]+, 437, 330, 274, 262, 256; (‒)-ESIMS m/z: 558 [M + Cl]−, 522 [M − H]−, 340, 296, 283, 242, 227; (+)-HRESIMS m/z: 546.4496 [M + Na]+ .White amorphous powder, 6 and 7 (each about 3 mg) were dissolved in 5% HCl-MeOH (3 mL), respectively, and then refluxed for 12 h at 80 °C. The reaction mixture was extracted with n-hexane (3 × 4 mL). The n-hexane portion was washed with H2O and concentrated in vacuo to yield methyl tetradecanoate and (R)-methyl 2-hydroxytetradecanoate, respectively. The H2O portion was neutralized with NH4OH, and then further concentrated in vacuo to yield the corresponding LCB with specific rotation 3).Compounds m/z 242 [M]+ (25), 211 [M − CH3]+ (11), 199 [M − COCH3]+ (22), 185 (8), 171 (4), 157 (7), 143 (22), 129 (9), 115 (4), 101 (9), 87 (61), 74 (100), 55 (24).Methyl tetradecanoate: EI-MS R)-Methyl 2-hydroxytetradecanoate: c 0.05, CHCl3); EI-MS m/z 258 [M]+ (7), 199 [M − COCH3]+ (65), 125 (30), 111 (56), 90 (47), 83 (85), 69 (100), 55 (92)., and were seeded to RPMI-1640 medium with 10% fetal bovine serum and 100 U/mL benzyl penicillin-streptomycin solutions, at 37 °C in a humidified atmosphere with 5% CO2/air for 24 h. Then the test samples were added and incubated at 37 °C for another 72 h. The detailed procedure for MTT assay can be found in our previous published literature [50 value using adriamycin as a positive control. Compounds 1), two new ceramides  and six known compounds  were identified from the marine bryozoan C. pallasiana. Among the isolated compounds, sterol 1 showed novelty in the C-23R methoxy group and double bond between C-24 and C-25 in its side chain. Since this is the first report of ceramides in this species, it can be considered important for its chemotaxonomic significance. Furthermore, ceramides with 14 carbons in the FAB were different from those we previously obtained from Bugula neritina [5) was found to exhibit stronger cytotoxicity than sterols and ceramides, suggesting that it could be responsible for the cytotoxicity of C. pallasiana.A new sterol (neritina . All com


These azulenyl-containing terpyridines showed fluorescent emission with a fluorescence quantum yield varying from 0.14, in the case of parent terpyridine, to 0.64 when methyl groups are grafted on the azulenyl seven-membered ring. According to the crystal structures and TDDFT calculations, different twisting of the aromatic constituents is responsible for the observed fluorescent behavior. The electrochemical profile contains one-electron oxidation/reduction steps, which can only be explained on the basis of the redox behavior of the azulene unit. The ability of the 4′-azulenyl 2,2′:6′,2″-terpyridine to bind poisoning metal cations was studied by UV–vis titrations using aqueous solutions of Hg(II) and Cd(II) chlorides as illustrative examples. This ability was exploited in the development of colorimetric “naked-eye” chemosensors for poisoning Hg(II) ions from drinking water in the presence of other metal pollutant competitors [4a for possible selective detection of poisoning metal ions. As representative examples, we have chosen Hg(II) and Cd(II) metal ions. UV–visible titration was performed by adding increasing amounts of a metal chloride aqueous solution into a methanol solution of ligand 4a  due to the possible formation of weak hydrogen bonds in this solvent [2 solution, the absorption maxima located at 378 nm and 431 nm are merging into a new band at 421 nm upon mercury complex formation. A progressive decreasing of the band located at 283 nm and the concomitant appearance of a new band around 315 nm were observed petitors . Therefo4.26 mM, . The ini solvent . For botobserved . It appe1H NMR titration of 4a with HgCl2 has been performed. The addition of 0.25 equivalents of the mercury salt to a solution of 4a in CD3OD (38 mM) caused the formation of a precipitate that it is insoluble in the deuterated methanol. Further addition of 0.25 equivalents of HgCl2 afforded a pale yellow solution with a brownish precipitate on the bottom of the NMR tube. After evaporation of this solvent, the solid was re-dissolved in DMSO-d6. The comparison with the 1H NMR spectrum of free 4a in the same deuterated solvent shows that the chemical shifts of all terpyridine and azulene protons are downfield shifted upon mercury complex formation 22+ are formed based on the metal ion.Both titrations show an isosbestic point (390 nm), suggesting that only two species  are present during the titration process. According to the observed saturation, it can be concluded that both M(terpyridine)Novel 4′-azulenyl-substituted terpyridines were efficiently synthesized following the Kröhnke methodology. The azulenylchalcone intermediates were conveniently synthesized using grind or microwave-assisted aldol condensation procedures. The target terpyridine compounds exhibit fluorescence emission upon excitation at the corresponding absorption maximum. The fluorescence quantum yield is influenced by the azulenyl substitution from 0.14 in the case of the parent 4′-azulenyl-2,2′:6′,2″-terpyridine to 0.64 for the trimethyl substituted azulenylterpyridine. According to the crystal structures, different twisting was observed that might be responsible for the observed fluorescent profile. The solid-state crystal packing showed π–π stacking interactions between the pyridine rings in face-to-face or T-shape orientation, completed by slipped-off π–π stacked azulenyl moieties according to their polarization vectors. TDDFT calculations showed that the fluorescence properties are determined by azulene-centered valence-state excitation and azulene→terpyridine charge-transfer transitions. Both compounds exhibit electrochemical behavior with one-electron oxidation/reduction steps, which can only be explained on the basis of the redox behavior of the azulene unit. The UV–vis titration studies proved that 4′-azulenyl-2,2′:6′,2″-terpyridine can bind poisoning Hg(II) and Cd(II) metal ions in aqueous environment, but with no clear color change as it has been expected.2Cl2 for fluorescence measurements was purchased from Merck. Dimethylformamide for cyclic voltammetry measurements was purchased from Sigma-Aldrich and kept over molecular sieves. Column chromatography was carried out on 40–63 mesh silica gel and aluminum oxide. Analytical thin-layer chromatography was performed on Merck silica gel 60 F254 plates. Visualization was accomplished with UV light and preliminary fluorescence emission was observed with 365 nm light on TLC spots. Starting azulene-1-carboxaldehydes were obtained following Vilsmeier reaction [3) containing TMS as internal standard with a Bruker Avance DRX 400  instrument; chemical shifts (δ) are expressed in ppm, and J values are given in Hz; Az denotes azulene protons. The splitting patterns are indicated as s, singlet; d, doublet; t, triplet; m, multiplet; td, triplet of doublets. Mass spectrometry was performed using a Varian 1200L Triple Quadrupole LC/MS/MS spectrometer by direct injection in ESI mode. Titrations were performed as constant host titrations (4.26 mM in methanol) at room temperature by the addition of aliquots of the respective metal chloride stock solution in methanol (working solution obtained by dilution with water). UV–vis spectra were recorded after each addition on a Varian Cary 100 spectrophotometer using 1 cm quarts cells and methanol/water as solvent. The fluorescence emission and excitation spectra were recorded with a Jasco FP-6500 spectrofluorometer equipped with a 150 W Xenon lamp. The excitation wavelength was 375 nm for 4a and 380 nm for 4b for working concentrations of 2.59 × 10−5 M. The fluorescence quantum yield was determined by comparison of diluted quinine bisulfate solution in 0.1 N H2SO4 (0.55 absolute quantum yield) [All reagents for performing the chemical reactions were used as received. CHm yield) . Electro2 [X-ray diffraction measurements were performed on a STOE IPDS II diffractometer, operating with Mo Kα (λ = 0.71073 Å) X-ray tube with graphite monochromator. The structures were solved by direct methods and refined by full-matrix least squares techniques based on F2 . The non4a: C25H17N3, M = 359.41 g∙mol−1, orthorhombic, P21cn, T = 200 K, a = 6.0110(4), b = 9.5419(6), c = 31.230(3) Å, α = β = γ = 90°, V = 1791.2(2) Å3, Z = 4, μ(Mo Kα) = 0.080 mm−1, F(000) = 752, R1obs = 0.0441, wR2obs = 0.1008, R1all = 0.0859, wR2all = 0.1398, GoF = 1.077, largest difference peak and hole: 0.218/−0.235 e∙A−3.Crystal data for compound 4b: C28H23N3, M = 401.49 g∙mol−1, monoclinic, C2/n, T = 293 K, a = 34.707(3), b = 8.7500(7), c = 14.8991(14) Å, α = γ = 90°, β = 105.906(8), V = 4351.4(7) Å3, Z = 8, μ(Mo Kα) = 0.073 mm−1, F(000) = 1696, R1obs = 0.0577, wR2obs = 0.0993, R1all = 0.1881, wR2all = 0.1438, GoF = 0.889, largest difference peak and hole: 0.138/−0.162 e∙A−3.Crystal data for compound (E)-3-(Azulen-1-yl)-1-(pyridin-2-yl)prop-2-en-1-one (2a): Route A. A neat mixture of 2-acetylpyridine , 1-azulencarboxaldehyde  and NaOH  were placed in a mortar and grinded for 10–15 minutes while a green-brownish solid is formed. The solid compound is washed with ether and the crude product was purified by column chromatography on silica gel (2% EtOH/CH2Cl2) to give compound 2a  as a green-brownish solid; IR (ATR) νmax: 3404, 3050, 2978, 1690, 1654, 1561, 1494, 1393 cm−1; 1H NMR  8.76 , 8.74 , 8.66 , 8.46 , 8.33 , 8.32 , 8.23 , 7.87 , 7.69 , 7.49–7.46 , 7.45 , 7.37 , 7.30 ; 13C NMR  189.3 (CO), 155.1 (Cq), 148.7 (CHPh-3), 145.1 (Cq), 140.1 (Cq), 139.0 (CHAz-6), 137.5 (CHAz-4), 136.9 (CHA=), 136.3 (CHPh-4), 135.6 (CHAz-2), 134.3 (CHAz-8), 126.4 (CHAz-7), 126.2 (CHAz-5), 125.8 (Cq), 125.6 (CHAz-3), 122.8 (CHB=), 120.4 (CHPh-5), 117.1 (CHPh-6); Anal. calcd for C18H13NO: C, 83.37; H, 5.05; N, 5.29; found: C, 83.3; H, 4.8; N, 5.3; MS : 242 (10%), 260 , 439 (25%), 502 (10%).Route B. To a stirred solution of azulen-1-carboxaldehyde  in ethanol (15 mL) was added 2-acetylpyridine  followed by the addition of NaOH . The reaction mixture was stirred at room temperature for 10–15 min. After that, diethyl ether (30 mL) was added and the formed precipitate filtered off. After column chromatography on silica gel as mentioned above, the desired chalcone was isolated .Route C. Azulen-1-carboxaldehyde , 2-acetylpyridine  and NaOH  were suspended in water (1.5 mL) in a microwave vial of 2 mL. The reaction mixture was introduced in a Biotage apparatus and irradiated for 15 min at 110 °C. After column chromatography on silica gel with 2% ethanol in dichloromethane chalcone 2a was isolated .(E)-1-(Pyridin-2-yl)-3-prop-2-en-1-one (2b): This compound was prepared following Route A described above for chalcone 2a by grinding neat 2-acetylpyridine  with 4,6,8-trimethylazulene-1-carbaldehyde  and NaOH . The crude product was purified by column chromatography (2% EtOH/CH2Cl2) to give compound 2b  as a red-brownish solid; IR (ATR) νmax: 3420 (br), 3042, 2980, 2864, 1690, 1563, 1492, 1351 cm−1; 1H NMR  9.00 , 8.74 , 8.22 , 8.20 , 8.13 , 7.85 , 7.46–7.43 , 7.40 , 7.30 , 3.18 , 2.86 , 2.61 ; Anal. calcd for C21H19NO: C, 83.69; H, 6.35; N, 4.65; found: C, 83.7; H, 6.5; N, 4.2.; MS : 302 , 367 (15), 423 (25%).4′-(1-Azulenyl)-2,2′:6′,2″-terpyridine (4a): A neat mixture of chalcone 2a (1.0 mmol), 2-acetylpyridine (2.0 mmol) and NaOH or KOH (2.0 mmol) are grinded in a mortar for around 10 min while a brick colored solid is formed. The resulting crude compound is introduced in a microwave vial together with ammonium acetate  and acetic acid (2.0 mL) and irradiated for 30 min at 160 °C. The resulting mixture is diluted with dichloromethane and purified by alumina column chromatography (5% petroleum ether/CH2Cl2) to give the title compound 4a  as blue-violet solid; mp 186–188 °C; λmax : 279 (4.58), 301 (sh), 377 (4.02); 1H NMR  8.78 , 8.74 , 8.71–8.67 , 8.36 , 8.26 , 7.84 , 7.62 , 7.45 , 7.32–7.30 , 7.26 , 7.20 ; 13C NMR  156.6 (Cq), 155.6 (Cq), 149.1 (CHtpy-3/3”), 147.0 (Cq), 142.7 (Cq), 138.4 (CHAz-6), 137.5 (CHAz-4/2), 136.7 (CHtpy-4/4”), 136.0 (Cq), 135.4 (CHAz-8), 128.5 (Cq), 124.5 (CHAz-7), 124.0 (CHAz-5), 123.6 (CHtpy-5/5”), 121.4 (CHtpy-6/6”), 121.3 (CHtpy-3’/5’), 118.0 (CHAz-3); Anal. calcd for C25H17N3: C, 83.54; H, 4.77; N, 11.69; found: C, 83.7; H, 4.5; N, 12.0.; MS : 360 , 361 (25%).4′--2,2′:6′,2″-terpyridine (4b): The title compound 4b was isolated following the above described procedure using 4,6,8-trimethylazulene-1-carbaldehyde . Compound 4b  was isolated as violet-black solid. mp >300 °C; λmax : 294 (4.61), 381 (2.73); 1H NMR,  8.70–8.67 , 8.52 , 7.86 , 7.73 , 7.37 , 7.33–7.30 , 7.10 , 7.04 , 2.92 , 2.63 , 2.60 ; 13C NMR  156.7 (Cq), 154.4 (Cq), 151.9 (Cq), 149.2 (CHtpy-3/3”), 147.3 (Cq), 146.3 (Cq), 145.9 (Cq), 138.3 (Cq), 136.7 (CHtpy-4/4”), 136.5 (CHAz-2), 132.0 (Cq), 130.1 (Cq), 129.5 (CHAz-7), 127.7 (CHAz-5), 123.6 (CHtpy-5/5”), 122.8 (CHtpy-3’/5’), 121.4 (CHtpy-6/6”), 115.4 (CHAz-3), 29.4 (CH3-6), 28.5 (CH3-4), 25.6 (CH3-8); Anal. calcd for C28H23N3: C, 83.76; H, 5.77; N, 10.47; found: C, 83.4; H, 5.2; N, 10.8; MS : 402 , 403 (30%).File 14a and 4b and overlay of the 1H NMR spectra of free 4′-azulenyl-2,2′:6′,2″-terpyridine and the corresponding mercury(II) complex.Computational details and the optimized geometries of the two 4′-azulenyl-2,2′:6′,2″-terpyridine compounds File 24a (CCDC 1420841).Crystallographic information file of compound File 34b (CCDC 1420842).Crystallographic information file of compound


Their structures were established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.A new epoxy-cadinane sesquiterpene, 4 Fraction VII, eluted with PE/EtOAc (2:1), was further purified by Sephadex LH-20 (CHCl3/CH3OH) and RP-18 (CH3OH/H2O 3:1) column chromatography and preparative TLC (PE/EtOAc 3:1) to afford 3 (11.0 mg), 5 (2.1 mg), 6 (14.0 mg), and 7 (8.0 mg). Fraction VIII, eluted also with PE/EtOAc (2:1), was further purified by Sephadex LH-20 (CHCl3/CH3OH) and RP-18 (CH3OH/H2O 3:1) column chromatography and preparative TLC (PE/EtOAc 1:4) to afford 2 (20.7 mg).Dried and powdered alga


Sphaerococcus coronopifolius collected from the rocky coasts of Corfu Island in the Ionian Sea yielded two new diterpene alcohols, sphaerollanes I, and II  featuring neodolabellane skeletons, and the new sphaeroane diterpene alcohol 16-hydroxy-9S*-acetoxy-8-epi-isosphaerodiene-2 (3), along with two previously reported metabolites 4, 5. The structures of the new natural products, as well as their relative stereochemistry, were elucidated on the basis of extensive spectral analysis, including 2D-NMR experiments.Investigation of minor metabolites in the extracts of the red alga  The presence of five sp2 carbon atoms in the molecule, as deduced from the 13C-NMR and DEPT spectra , a trisubstituted olefinic bond , an exomethylene , and a primary alcohol . Extensive analyses of the 2D-NMR data of 3 including COSY, HSQC and HMBC spectra led to the unambiguous assignment of all protons and carbons on the sphaeroane skeleton. The H2-16 oxygenated methylene protons at δH 3.99 (br. s) showed heteronuclear long range couplings to C-10 (δC 32.7), C-11 (δC 133.5), and C-12 (δC 127.4), which confirmed the presence of the primary allylic alcohol at C-11. Correlations from H-8 methine (δH 2.74) and both H2-10 (δH 2.59 and 2.04) to C-9 (δC 68.7), as well as from H-9 (δH 5.35) to the carbonyl signal at δC 170.8 required the acetyl group to be positioned at C-9. The olefinic proton H-12 (δH 5.68) showed HMBC correlations to C-8 (δC 51.3) and C-13 (δC 41.6), thus positioning both the double bond and the acetate group next to the 6-membered ring junctions. The H2-17 olefinic methylene protons at δH 4.79 (br. s) correlated with C-6 (δC 30.8), C-7 (δC 149.4), and C-8 (δC 51.3), had to be placed on C-7. Long range heteronuclear couplings from H2-6 (δH 2.23 and 2.22) to both C-4 (δC 46.4) and C-5 (δC 38.9), and from H2-5 (δH 1.87 and 1.48) to C-7 (δC 149.4) were observed in the HMBC spectrum. The H3-15 methyl signal at δH 0.76 showed correlations to C-3 (δC 58.0), C-4 (δC 46.4), C-5 (δC 38.9), and C-14 (δC 53.7), and was placed on the quaternary carbon C-4. The cycloheptane ring was completed by the HMBC correlation observed between H-8 (δH 2.74) and C-14 (δC 53.7). The correlation of both H3-19 and H3-20 (δH 0.82 and 0.92) with C-3 (δC 58.0) and C-18 (δC 29.8), required the presence of the isopropyl group at C-3. The correlations observed between H-1α (δH 1.25) and C-13 (δC 41.6), and between H-2b (δH 1.28) and C-18 (δC 29.8), confirmed the place of methylene carbons C-1 and C-2 in the 5-membered ring.-16-hydroxy-9-acetoxy-8-epi-isosphaerodiene-2 (3)  .4) + (3), 306 [M-CH2CO]+ (29), 288 [M-AcOH]+ (37), 270 [M-AcOH-H2O]+ (44), 255 [M-AcOH-H2O-Me]+ (20), 245 [M-AcOH-iPr]+ (72), 227 [M-AcOH-H2O-iPr]+ (71), 199 (17), 171 (31), 133 (45), 91 (69), 43 [CH3CO]+ (100); HRFAB-MS (m/z): 349.2732 [M+H]+ .Colorless oil; [α]D +5.5 ; UV (CHCl3) λmax (log ɛ) 250 (1.76) nm; IR (CHCl3) νmax 3,422, 1,728, 1,240, 1,014, 973 cm−1; NMR data (CDCl3), see 2O]+ (1), 289 [M+H-AcOH]+ (11), 271 [M+H-AcOH-H2O]+ (38), 255 [M+H-AcOH-H2O-Me]+ (9), 245 [M+H-AcOH-iPrH]+ (14), 227 [M+H-AcOH-H2O-iPrH]+ (8), 173 (14), 147 (9), 119 (11), 105 (8), 60 [AcOH]+ (100); HRFAB-MS (m/z): 348.2674 [M]+ .Colorless oil; [α]D +10.3 ; UV (CHCl3) λmax (log ɛ) 244 (1.95) nm; IR (CHCl3) νmax 3,367, 1,733, 1,240, 1,024, 888 cm−1; NMR data (CDCl3), see + (1), 329 [M+H-H2O]+ (9), 287 [M+H-AcOH]+ (29), 269 [M+H-AcOH-H2O]+ (100), 255 [M+H-AcOH-CH2OH]+ (11), 243 [M+H-AcOH-iPrH]+ (8), 225 [M+H-AcOH-H2O-iPrH]+ (12), 213 [M+H-AcOH-CH2OH-iPr]+ (7), 171 (14), 145 (13), 137 (16), 105 (13), 60 [AcOH]+ (38); HRFAB-MS (m/z): 347.2586 [M+H]+ .Colorless oil; [α]


III atom in the title compound, (C11H7N2O)[AuCl4]·C11H6N2O, is in a nearly square-planar environment defined by four Cl atoms. The protonated 9-oxo-4,5-diazafluoren-4-ium cation forms an N—H⋯N hydrogen bond with the neutral 4,5-diazafluoren-9-one molecule.The Au DOI: 10.1107/S1600536809006734/hy2184Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


N-formyl-Met-Leu-Phe-OH (1) is described. After Fmoc solid phase peptide synthesis, on-bead formylation and HPLC purification, more than 30 mg of the fully 13C/15N-labelled tripeptide 1 could be isolated in a typical batch. This peptide can be easily crystallised and is therefore well suited as a standard sample for setting up solid-state NMR experiments.A mild synthetic method for  It should contain a number of molecular groups with different chemical shifts for setting up correlation spectra. The 13C/15N-labelled tripeptide N-formyl-Met-Leu-Phe-OH (f-MLF-OH) (1) has been shown in a number of solid-state NMR studies to fulfil these criteria. It has been used in great detail to examine spin dynamics in peptide and for distance measurements . Fu. Fu13C/1DIC/HOBt –17. The obtain 5 . The mainditions –20, whicwith TFA –22. To pwith TFA –24.13C/15N-labelled formylated Met-Leu-Phe tripeptide as carboxylic acid in acceptable yields [32.8 mg (23%) after HPLC purification]. Due to the selected reagents, i.e. MSNT for the esterification, DIC/HOBt for the peptide coupling and ethyl formate for the formylation, shorter reaction time and quantitative conversion could be accomplished when compared to the previous protocol from 1976  was added to the syringe. After shaking (3 × 90 min), the liberated peptide was filtered off into Millipore™ water. This solution was lyophilised and the residue was purified by HPLC. Yield: 32.8 mg (23%).R = 21.08 min; isocratic: Lichrospher RP8 (Merck), 125 × 4.0 mm, 5 µm, 0.1% TFA/MeCN (66:34), 0.8 mL/min, tR = 5.07 min.HPLC conditions: Preparative: Reprosil AQ, 250 × 20, 10 µm, 0.1% TFA/MeCN (100:60), 10 mL/min; analytical: gradient: Reprosil AQ, 125 × 4.6 mm, 5 µm, 0.8 mL/min, t13C NMR : 173.5 , 172.6 , 171.8 , 162.8 , 138.0 , 131.1-126.8 , 55.1-51.3 , 41.3 , 37.8 , 32.4 , 30.4 , 25.4 , 23.2 , 21.7 , 15.3 .m/z (%) = 460.3 (100.0) [M–H]–, 13C21H3115N3O5S calcd. 461.26.MS (ESI): 13C NMR and 13C/15N MAS-NMR spectra of f-MLF-OH (1) are available in the Supporting Information.Procedures for colourimetric resin tests , crystallisation protocol, ESI, File 113C/15N-labelled tripeptide N-Formyl-Met-Leu-Phe, useful as a reference in solid-state NMR spectroscopy.A practical synthesis of the


Their structures were established by detailed MS and NMR spectroscopic analysis, as well as comparison with literature data.Two new brominated selinane sesquiterpenes, 1-bromoselin-4(14),11-diene ( Dictyopteris divaricata, found widely spread along the coasts of China, has provided many structurally interesting sesquiterpenes and norsesquiterpenes +, which indicated that the mixture was composed of three compounds. The 1H- and 13C-NMR data of these three compounds 1–3 could be distinguished with the aid of the NMR data shown in Compounds m/z 198 was tentatively identified as cadalene (3) by comparison with the EIMS database + correspond to the other two compounds 1–2, whose molecular formulae were determined as C15H23Br on the basis of HRESIMS .The compound with the molecular ion peak at database . Fortuna spectra . H-2 was1H-NMR spectrum of 1 displayed two methyl singlets, one double-doublet assignable to a halogenated/oxygenated methine, and four broad characteristic olefinic protons singlets. The 13C-NMR spectrum along with the DEPT and HSQC experiments revealed the presence of two methyls, seven methylenes, three methines, and three quaternary carbon atoms. A detailed comparison of the NMR data with those reported for β-selinene (5) and β-dictyopterol (6) revealed the similarity between them , as established by comparison with the reported data for 1-bromo-4-hydroxyselin-7-ene [m/z 282/284 (1:1) [M]+ and fragment ion peak at m/z 203 [M–Br]+ in the EIMS and the molecular formula C15H23Br. The observed HMBC correlations from H-12 to C-7 and C-13, from H-13 to C-7, C-11, and C-12, from H-14a and H-14b to C-3 and C-5, and from H-15 to C-1, C-5, C-9, and C-10 confirmed the planar structure of 1.The yopterol  revealedeen them , althoug1 was determined by analysis of coupling constants and NOESY correlations, as well as by comparison with literature data. H-1 was axial, as indicated by its large coupling constant (11.8 Hz), and located on the same face of H-5 from the NOESY correlation between them. The NOESY correlations between H-15/H-2a, H-6a, H-8a indicated C-15, H-2a, H-6a, and H-8a to be axial and the decalin ring to be trans-fused. C-11 was equatorial and the configuration at C-7 was the same as in 4–7 based on their identical NMR data and the observed NOESY correlation between H-7/H-9a + and fragment ion peaks at m/z 203 [M–Br]+ in the EIMS and the molecular formulae C15H23Br, compound 2 should be an isomer of 1, a fact conformed by analysis of their NMR data. The NMR data were also compared with those reported for β-selinene (5), showing the similarity between them  to give ten fractions, I-X. Fraction I, eluted with PE, was further purified by silica gel column chromatography (PE) to afford a mixture of 1–3 (10.0 mg) and a mixture of 4 and 5 (40.9 mg). Fraction VII, eluted with PE/EtOAc (2:1), was further purified by Sephadex LH-20 (CHCl3/CH3OH) and RP-18 (CH3OH/H2O 3:1) column chromatography and preparative TLC (PE/EtOAc 3:1) to afford 6 (5.1 mg). Fraction IX, eluted with EtOAc, was further purified by Sephadex LH-20 (CHCl3/CH3OH) and RP-18 (CH3OH/H2O 9:1) column chromatography and preparative TLC (EtOAc) to afford 7 (5.5 mg).Dried and powdered alga 1-Bromoselin-4(14),11-diene (1). Colorless oil; 1H-NMR and 13C-NMR: see m/z (relative intensity): 284/282 [M]+ (3), 203 [M–Br]+ (98), 161 (26), 159 (28), 147 (88), 133 (36), 119 (52), 105 (89), 91 (100), 79 (54), 77 (46), 67 (37)9-Bromoselin-4(14),11-diene (2). Colorless oil; 1H-NMR and 13C-NMR: see m/z (relative intensity): 284/282 [M]+ (2), 203 [M–Br]+ (59), 161 (26), 159 (11), 147 (61), 133 (28), 119 (44), 105 (78), 91 (100), 79 (56), 77 (52), 67 (46).Cadalene (3). Colorless oil; 1H-NMR and 13C-NMR: see m/z (relative intensity): 198 (59), 183 (100), 168 (48), 153 (16).1–3: 3,074, 2,931, 2866, 1,643, 1,604, 1,512, 1,450, 1,377, 887 and 829 cm−1.IR (KBr) of


N,N-dipyrid-2-yl)carbamide (M1) was copolymerized with exo,exo-[2-(3-ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-en-2-carbonyloxy)ethyl]trimethylammonium iodide (M2) using the Schrock catalyst Mo(CHCMe2Ph)(OCMe(CF3)2)2[Mo] to yield poly(M1-b-M2). In water, poly(M1-b-M2) forms micelles with a critical micelle-forming concentration (cmc) of 2.8 × 10−6 mol L−1; Reaction of poly(M1-b-M2) with [Rh(COD)Cl]2  yields the Rh(I)-loaded block copolymer poly(M1-b-M2)-Rh containing 18 mg of Rh(I)/g of block copolymer with a cmc of 2.2 × 10−6 mol L−1. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH3CON(Py)2RhCl(COD) . Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.e. an increase in the n:iso ratio was accomplished, which could be further enhanced by the addition of excess ligand, e.g., triphenylphosphite. Special features of the micellar catalytic set up are discussed.Norborn-5-ene-( I and IrI complexes of N,N-dipyrid-2-ylacetamide and their use in hydroformylation reactions hept-5-ene-2-carbonyloxy)ethyl]trimethylammonium iodide (M2) was prepared in a four-step procedure ethan-1-ol, conversion of the free carboxylic acid 1 into the corresponding acid chloride with SOCl2 and reaction of the acid chloride with dry ethanol to form the diester 2. Finally, compound 2 was converted into M2 via quaternization of the tertiary amine with methyl iodide.The synthesis of norborn-5-ene-, required special attention. Though M1 contains a chelating ligand and can be polymerized by both Schrock and Grubbs-type initiators [OCMe(CF3)2]2 ([Mo]) ) .M1 and M2 by the action of [Mo] proceeded smoothly at room temperature. Conversion of monomer M1 reached 100% after 10 min   and the poly(M2) block, respectively.Both the homopolymerization of igure S2  and indiM1-co-M2) was determined by fluorescence spectroscopy [p-toluidene-2-naphthylsulfonic acid (10−6 mol/L) was used as the fluorescence probe. A cmcwater for poly(M1-b-M2) of 2.8 × 10−6 mol L−1 was determined  was loaded with Rh(I) via reaction of poly(M1-b-M2) with [RhCl(COD)]2  to yield poly(M1-b-M2)-Rh (M1) [OCMe(CF3)2]2[Mo] hept-5-en-2-carbonyloxy)ethyl]trimethylammonium iodide (M2) exo,exo-7-Oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid mono(2-dimethylaminoethyl) ester (1):exo-3,6-Epoxy-1,2,3,6-tetrahydrophtalic anhydride , 2-dimethylaminoethanol  and p-toluenesulfonic acid  were dissolved in 120 mL of THF and stirred at room temperature for 8 h. The white precipitate was filtered, washed with diethyl ether and dried to afford a white solid; yield: 13.8 g (90.0%). 1H NMR (CDCl3): δ 2.70 , 2.78–2.81 , 3.01 , 3.12 , 4.37 , 4.51 , 5.24 , 6.37 , 6.47 .exo,exo-7-Oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid 2-(2-dimethylaminoethyl) ester 3-ethyl ester (2):1  was dissolved in 20 mL of EtOH (c = 0.2 M). SOCl2  was added dropwise at room temperature and the reaction mixture was stirred at room temperature for 8 h. The solvent was removed in vacuo, the green residue dissolved in 25 mL of CH2Cl2 and washed with 10 mL of sat. NaHCO3 solution. The aqueous phase was extracted with CH2Cl2 (3 × 10 mL) and the combined organic layers were dried over MgSO4. Finally, the solvent was removed under reduced pressure to afford a yellow oil; yield: 695 mg (60%). 1H NMR (CDCl3): δ 1.29 , 2.30 , 2.59 , 2.81 , 2.88 , 4.16–4.21 , 4.23–4.28 , 5.28 , 5.29 , 6.47 .exo,exo-[2-(3-Ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonyloxy)ethyl]trimethylammonium iodide (M2):2  was dissolved in 2 mL of CH3I at 0 °C. The reaction mixture was stirred for 30 min at 0 °C and for 8 h at room temperature. The resulting yellow precipitate was isolated by filtration, dried and recrystallized from boiling ethanol. The crude product was dissolved in CH2Cl2 and precipitated with hexane to afford a white solid; yield: 875 mg (88%). 1H NMR (CDCl3): δ 1.30 , 2.86 , 2.94 , 3.54 , 4.16 , 4.10–4.23 , 4.56 , 4.74 , 5.15 , 5.43 , 6.48 , 6.50 . 13C NMR : δ 14.24 (CH3), 46.77 (CH), 47.91 (CH), 54.88 (CH3), 58.65 (CH2), 61.69 (CH2), 64.75 (CH2), 80.10 (CH), 80.87 (CH), 136.52 (CH), 136.76 (CH), 171.19 (Cq), 172.00 (Cq). IR (ATR) ν (cm−1) = 3433 (w), 3002 (w), 2977 (w), 1732 (ss), 1190 (ss), 1157 (ss) 913 (s), 887 (s). Elemental analysis: calcd. for C15H24INO5: C, 42.36; H, 5.69; N, 3.29; found: C, 42.25; H, 5.71; N, 3.29.Homopolymerization of M1: M1  was dissolved in 5 mL of CH2Cl2 and treated with a solution of [Mo]  in 1 mL of CH2Cl2. The yellow reaction mixture was stirred for 2 h at room temperature. A solution of ferrocene carboxaldehyde (10-fold excess based on initiator) in CH2Cl2 was added and the mixture was stirred for 1 h at room temperature. The polymer was precipitated by addition of pentane, filtered off, thoroughly washed with pentane and dried; yield: 85 mg (85%). Poly(M1): Mn = 29400 g mol−1, Mn(found) = 37900 g mol−1; PDI = 1.21. 1H NMR (CDCl3): δ 8.39 , 7.72 , 7.34 , 7.14 , 5.72–5.43 , 3.12 , 2.89–2.23 , 2.20–1.20 . 13C NMR (CDCl3): δ 175.0 (C=O), 154.8, 148.9, 137.8, 134.6 and 130.2 , 122.6 and 121.9 (-CH=CH-), 53.3, 47.6, 41.9 and 37.3 . FT-IR (ATR mode): ν (cm−1) = 2995 (w), 1672 (s), 1577 (s), 1426 (m), 1239 (w), 1048 (m), 739 (m).Homopolymerization of M2: M2  was dissolved in 5 mL of CH2Cl2 and treated with a solution of [Mo]  in 1 mL of CH2Cl2. The resulting white cloudy reaction mixture was stirred for 2 h at room temperature. A solution of ferrocene carboxaldehyde (10-fold excess based on initiator) in CH2Cl2 was added and the mixture was then stirred for 1 h at room temperature. The polymer was filtered off, thoroughly washed with pentane and dried; yield: 90 mg (90%). Poly(M2): Mn = 23600 g mol−1, Mn(found) = 24500 g mol−1, PDI = 1.36. 1H NMR (CDCl3): δ 5.83 , 5.17 , 4.70 , 4.21 , 3.51 , 1.26 . 13C NMR (CDCl3): δ 171.3 and 170.4 (C=O), 132.7(-CH=CH-), 77.2 (NBE), 64.6, 61.8, 59.4 (CH2), 55.1, 53.8 and 52.9 (NCH3), 14.1 (CH3). FT-IR (ATR mode): ν (cm−1) = 3428 (w), 2969 (w), 1726 (s), 1427 (m), 1181 (w), 1018 (m), 953 (m).Synthesis of poly(M1-b-M2): A solution of [Mo]  in 1 mL of CH2Cl2 was added to one of M1  in 1 mL of CH2Cl2. The reaction mixture was stirred for 20 min and a small amount was withdrawn for GPC measurements. M2  was dissolved in 2 mL of CH2Cl2 and this solution was added to the reaction mixture. The resulting white cloudy reaction mixture was stirred for another 90 min. The polymerization was terminated with ferrocene carboxaldehyde (10-fold excess based on initiator) and the reaction was stirred for a further hour. The polymer was filtered off, thoroughly washed with pentane and dried; yield: 100 mg (76%). Mn = 44100 g mol−1, Mw = 61100 g mol−1, PDI = 1.38. 1H NMR (CDCl3): δ 8.40, 7.92, 7.43, 7.33 , 5.79 , 5.17 , 4.70 , 4.21 , 3.51 , 1.87 , 1.27 (CH3). 13C NMR (CDCl3): δ 175.6 (C=O), 171.3 and 170.4 (C=O), 154.8, 148.9, 137.8, 134.6 and 130.2 , 122.8 and 122.2 (-CH=CH-), 77.0 (NBE), 64.6, 61.6, 59.3 (CH2), 52.8 (NCH3), 22.3, 14.1 (CH3). FT-IR (ATR mode): ν (cm−1) = 3404 (w), 2937 (w), 1727 (s), 1679 (m), 1586 (m), 1467 (m), 1432 (w), 1375 (m), 1238 (w), 1184 (s), 1097 (w), 1018 (m), 954 (m), 749 (m).Synthesis of poly(M1-b-M2)-Rh: [Rh(COD)2Cl]2 (8 mg) was dissolved in CH2Cl2. This solution was added dropwise to a suspension of poly(M1-b-M2) (100 mg) in 5 mL of CH2Cl2. The mixture was stirred for 10 h at room temperature; then the polymer was filtered off, thoroughly washed with pentane and dried; yield: 100 mg (92%). The Rh-content was determined by ICP-OES: 18 mg Rh/g copolymer .cmc determination of poly(M1-b-M2) and poly(M1-b-M2)-Rh: The cmc in water were determined by fluorescence spectroscopy [p-toluidene-2-naphthylsufonic acid (10−6 M) as the fluorescence probe. Polymer solutions were prepared in a concentration range from 1 × 10−4–1 × 10–13 mol L–1. cmc of poly(M1-b-M2) = 2.8 × 10−6 mol L−1; cmc of poly(M1-b-M2)-Rh = 2.2 × 10−6 mol L−1.troscopy  using 6-Quantification of Rh: The amount of Rh bound to the block copolymers or leached into the products was determined by dissolving a 20.0 mg amount of the polymer or the product mixture in aqua regia (25 mL). Rh was quantified by ICP-OES at λ = 343.489 nm, measuring the background at λ1 = 343.410 and λ2 = 343.600 nm, respectively. A 1000 ppm Rh standard  was used to prepare standards of 0, 0.100, 1.00 and 10.00 ppm.General procedure for hydroformylation: The reaction was carried out in a 300 mL Parr high-pressure reactor. The reactor was evacuated, flushed with argon and filled with the catalyst, water or toluene (30 mL), and 1-octene , leading to a substrate to catalyst ratio of 5000:1. tert-Butylbenzene (1.00 mL) was added as internal standard. To purge the reactants, the mixture was pressurized with a 1:1 mixture of CO and H2 up to a pressure of 30 bar and then the pressure was released. Finally, the pressure was adjusted to 50 bar with the aid of a back pressure regulator. The autoclave was heated to 70 °C and kept at this temperature. Samples were taken every 30 min. The isomeric 1-octenes and aldehydes were identified and quantified by their MS spectra as well as by their retention times using commercially available compounds as reference material.Recyclability studies with poly(M1-b-M2)-Rh: Hydroformylations were carried out as described above. For recycling, the product was extracted with diethyl ether (4 × 10 mL). Fresh 1-octene , and tert-butylbenzene (1.0 mL) were added to the aqueous, catalyst-containing phase and the reaction was run under the same conditions as before. The TONs in two consecutive cycles as determined by GC-MS were 4300 and 3900, respectively.M1 by the action of Mo(CHCMe2Ph)(OCMe(CF3)2)2, GPC-traces (DMF) of poly(M1) and poly(M1-b-M2); cmc measurements for poly(M1-b-M2) and poly(M1-b-M2)-Rh in water; conversion of 1-octene, product formation, product distribution in the hydroformylation of 1-octene in toluene in the presence of C1,C1 and triphenylphosphite; n:iso selectivities for catalysts poly(M1-b-M2)-Rh) and poly(M1-b-M2)-Rh with triphenylphosphite as a function of conversion.Supporting Information contains polymerization kinetics of File 1Graphical representations of measurements.


Nicotiana tabacum glycosylated benzophenone to three glycosides, 4-O-β-D-glucopyranosylbenzophenone (9%), diphenylmethyl β-D-glucopyranoside (14%), and diphenylmethyl 6-O-(β-D-glucopyranosyl)-β-D-glucopyranoside (12%) after 48 h incubation. On the other hand, incubation of benzophenone with immobilized cells of N. tabacum in sodium alginate gel gave products in higher yields, i.e. the yields of 4-O-β-D-glucopyranosylbenzophenone, diphenylmethyl β-D-glucopyranoside, and diphenylmethyl 6-O-(β-D-glucopyranosyl)-β-D-glucopyranoside were 15, 27, and 22%, respectively. Bisphenol A was converted into three glycosides, 2,2-bis(4-β-D-glucopyranosyloxyphenyl)propane (16%), 2-(4-β-D-glucopyranosyloxy-3-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl) propane (8%), and 2-(3-β-D-glucopyranosyloxy-4-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl)propane (5%). Also the use of immobilized N. tabacum cells improved the yield of products; the glycosylation of bisphenol A with immobilized N. tabacum gave 2,2-bis(4-β-D-glucopyranosyloxyphenyl)propane (24%), 2-(4-β-D-glucopyranosyloxy-3-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl) propane (15%), and 2-(3-β-D-glucopyranosyloxy-4-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl)propane (11%).Benzophenone and bisphenol A are environmental pollutions, which have been listed among “chemicals suspected of having endocrine disrupting effects” by the World Wildlife Fund, the National Institute of Environmental Health Sciences in the USA and the Japanese Environment Agency. The cultured cells of  Use of plant cell culture is a new approach to biotransformation research. Furthermore, biological potential of plant cell culture to biotransform exogenously added toxic compounds has attracted much attention in pollution control.7Nicotiana tabacum in sodium alginate gel.Benzophenone and bisphenol A are widely used as the starting material for the production of polyacrylates, ether resins, phenol resins, insecticides, agricultural chemicals, pharmaceuticals, and coatings, and are released as pollutants and toxic compounds into the environment.1H and 13C NMR, H-H COSY, C-H COSY, and HMBC spectra were recorded using a Varian XL-400 spectrometer in CD3OD solution. The chemical shifts were expressed in δ (ppm) referring to TMS. The FABMS spectra were measured using a JEOL MStation JMS-700 spectrometer. Cultured plant cells of N. tabacum have been cultivated over 20 years in our laboratory and subcultured in 300 ml conical flasks containing Murashige and Skoog’s medium  on a rotary shaker (120 rpm) at 25 °C in the dark for every 3–5 weeks.Benzophenone and bisphenol A were purchased from Aldrich Chemical Co. The N. tabacum was added 15 mg of substrate. The cultures were incubated at 25 °C for 48 h on a rotary shaker (120 rpm) in the dark. After the incubation period, the cells and medium were separated by filtration with suction. The filtered medium was extracted with EtOAc. The cells were extracted (x3) by homogenization with MeOH, and the MeOH fraction was concentrated and partitioned between H2O and EtOAc. The EtOAc fractions were combined, concentrated, and analyzed by HPLC . The H2O fraction was applied to a Dianion HP-20 column and the column was washed with H2O followed by elution with MeOH. The MeOH eluate was subjected to preparative HPLC  to give products. The yield of the products was determined on the basis of the peak area from HPLC and expressed as a relative percentage to the total amount of the whole reaction products extracted.To the 500 ml flask containing the suspension cultured cells of O-β-D-glucopyranosylbenzophenone (2): m/z 361 [M+H]+; 1H NMR : δ 3.73 , 3.92 , 5.05 , 7.20 , 7.50 , 7.60 , 7.70 , 7.77 . Diphenylmethyl β-D-glucopyranoside (3): FABMS: m/z 369 [M+Na]+; 1H NMR : δ 3.67 , 3.88 , 4.27 , 6.05 , 7.18 , 7.23 , 7.33 , 7.39 , 7.47 . Diphenylmethyl 6-O-(β-D-glucopyranosyl)-β-D-glucopyranoside (4): FABMS: m/z 531 [M+Na]+; 1H NMR : δ 3.66 , 3.81 , 3.86 , 4.15 , 4.30 , 4.45 , 6.05 , 7.18 , 7.26 , 7.33 , 7.40 , 7.51 . 2,2-Bis(4-β-D-glucopyranosyloxyphenyl)propane (6): FABMS: m/z 575 [M+Na]+; 1H NMR : δ 1.61 , 4.87 , 6.98 , 7.13 . 2-(4-β-D-Glucopyranosyloxy-3-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl)propane (7): FABMS: m/z 591 [M+Na]+; 1H NMR : δ 1.60 , 4.70 , 4.86 , 6.66 , 6.68 , 6.98 , 7.08 , 7.14 . 2-(3-β-D-Glucopyranosyloxy-4-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl)propane (8): FABMS: m/z 591 [M+Na]+; 1H NMR : δ 1.60 , 4.60 , 4.88 , 6.72 , 6.81 , 6.90 , 7.00 , 7.16 .Spectral data of products: 4-N. tabacum (100 g) in the stationary growth phase were added to this solution and the mixture was stirred for 2 h until it became homogeneous. The suspension was added dropwise from a dropping funnel with a glass tube into a 5% CaCl2 solution (1 L) with stirring to form pieces of spherical sodium alginate gel with 5 mm diameter immediately. After washing with water, immobilized N. tabacum cells were used for biotransformation of benzophenone and bisphenol A.Sodium alginate (2%) was suspended in water (500 ml), which was autoclaved at 120 °C for 30 min. Cultured cells of N. tabacum cells which included 30 g of N. tabacum cells with 100 ml of MS medium containing 3% sucrose in a 500 ml conical flask was added 15 mg substrate. The flask was stirred at 25 °C for 48 h on a rotary shaker (120 rpm) in the dark. Products were extracted from the cells and were purified by the same method as described above.To 150 ml of the immobilized N. tabacum, which had been treated with benzophenone (1) for 48 h. No products were observed in the medium. Three potentially glycosylated products 2–4 were obtained, and no additional conversion products such as hydroxylated and reduced products were observed in spite of the careful HPLC analyses. The chemical structures of the products were determined on the basis of their FABMS, 1H and 13C NMR, H-H COSY, C-H COSY, and HMBC spectra as 4-O-β-D-glucopyranosylbenzophenone , diphenylmethyl β-D-glucopyranoside , and diphenylmethyl 6-O-(β-D-glucopyranosyl)-β-D-glucopyranoside   .N. tabacum cells to biotransform benzophenone (1), the time course in the conversion of 1 was followed. 1) was converted into 3 at early stage of incubation, and that the product 4 was accumulated in the cells after 24 h incubation. This result indicated that formation of disaccharide 4 occurred following to that of glucoside 3.In order to examine the ability of cultured 1) by immobilized N. tabacum cells with sodium alginate was investigated. To examine the effect of sodium alginate concentration on the glycosylation of benzophenone (1), the cells were immobilized with sodium alginate at final concentrations of 1, 2, 3, 4, and 5%. N. tabacum cells, which had been prepared at 2% sodium alginate concentration, were used for biotransformation experiments. After 48 h incubation of benzophenone (1), 4-O-β-D-glucopyranosylbenzophenone , diphenylmethyl β-D-glucopyranoside , and diphenylmethyl 6-O-(β-D-glucopyranosyl)-β-D-glucopyranoside  were obtained in higher yields in comparison with the case of the biotransformation using normal cells (1) was higher than that in the case of the time course of the biotransformation using normal cells.Next, the conversion of benzophenone , 2-(4-β-D-glucopyranosyloxy-3-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl) propane , and 2-(3-β-D-glucopyranosyloxy-4-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl)propane  were isolated from cultured N. tabacum cells treated with bisphenol A (5) after 48 h-incubation  with immobilized N. tabacum cells gave 2,2-bis(4-β-D-glucopyranosyloxyphenyl)propane , 2-(4-β-D-glucopyranosyloxy-3-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl) propane , and 2-(3-β-D-glucopyranosyloxy-4-hydroxyphenyl)-2-(4-β-D-glucopyranosyloxyphenyl) propane   propane  .N. tabacum can convert benzophenone and bisphenol A into three glycosides, respectively. In the time course experiment, it was found that reduction of benzophenone first occurred, followed by glycosylation of the newly generated hydroxyl group. The yield of glycosides produced from benzophenone by immobilized N. tabacum cells in sodium alginate gel was improved in comparison with the case of biotransformation by cultured N. tabacum cells. Total yield of glycosides of benzophenone produced by immobilized N. tabacum cells was about 1.8 times higher than that of products obtained in normal biotransformation experiment. The use of immobilized cells of N. tabacum for conversion of bisphenol A also enhanced the yield of the products, that is, the total yield of glycosides was about 1.7 fold higher than that of products obtained in normal biotransformation experiment.This study demonstrated that the cultured plant cells of N. tabacum can incorporate the endocrine-disrupting chemicals such as benzophe-none and bisphenol A to biotransform into glycosides, and can lower their concentration in the medium. The immobilized cells of N. tabacum would be useful to detox industrial by-products, i.e. benzophenone and bisphenol A, to stable glycosides. This procedure is a simple operation and is environmentally friendly. Further studies on the enzymes which catalyze the glycosylation of benzophenone and bisphenol A are now in progress.The results of this experiment revealed that plant cells of


It is chelated by two 1,10-phenanthroline ligands, a 2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate monoanion and a 4-oxido-2-oxo-1,2-dihydropyrimidine-5-carboxylate dianion. The H atom involved in an N—H⋯N hydrogen bond between the 1,2-dihydropyrimidine units has half occupancy and is disordered around a twofold rotation axis.In the title compound, [Y(C DOI: 10.1107/S1600536808025701/gk2161Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The age groups used for analysis were 18-20, 21-29, 30-39, 40-49, 50-64, and 65 or older instead of 18-20, 21-30, 31-40, 41-50, 51-60, and 61 or older. The authors regret this error. Corrections to the text and tables were made to our Web site on August 15, 2010, and appear online at www.cdc.gov/pcd/issues/2010/may/09_0123_es.htm.En el artículo "Factores asociados a la detección del cáncer de cuello uterino en Puerto Rico" se notificaron incorrectamente las categorías de los grupos de edades usadas para el análisis. Los grupos de edades usados para el análisis fueron 18-20, 21-29, 30-39, 40-49, 50-64 y 65 o más, en vez de 18-20, 21-30, 31-40, 41-50, 51-60 y 61 o más. Los autores lamentan este error. Las correcciones en el texto y en las tablas se hicieron en nuestro sitio web en agosto 15, 2010 y se encuentran en Internet en


Furthermore, both anthryl esters were used to synthesize symmetric iron(II)-bis(terpyridine)complexes 6a–b. Irradiation experiments were carried out with both the free ligands and an iron(II)-complex in order to investigate the photochemistry of the compounds.The synthesis of several symmetrically 4,4″-functionalized 2,2′:6′,2″-terpyridines is reported. In addition to the biscarboxylic acid 4,4″-tpy(CO The special  properties of their metal complexes have led to the development of various luminescent metal compounds  and sensBecause of this impact of terpyridine derivatives in photochemistry, we focused our attention on the synthesis and studies of potentially photoswitchable terpyridine ligands. The synthesis of bisterpyridines linked by a diazogroup has been reported –8. As we3, starting from methyl 2-acetylisonicotinate (1) and 4-tert-butylbenzaldehyde (2), by a one-pot combination of a Kröhnke type condensation and subsequent hydrolysis of the ester groups, similar to a synthetic route recently described in the literature . Thus, Mukaiyama acid activation of 3 with 2-chloro-N-methylpyridinium iodide in the presence of triethylamine with an excess of the anthryl alcohol (3–5 equiv) gave the desired terpyridine-4,4″-esters 5a and 5b in yields up to 75% (The diacid p to 75% .5a)2](PF6)2 (6a) and [Fe(5b)2](PF6)2 (6b) by reaction of ferric chloride tetrahydrate with the corresponding terpyridines in methanol solution (We then synthesized the iron(II)-complexes -cycloadducts cannot be distinguished from the reagents, because their molecular formulas and hence their molecular masses are identical.NMR- and MALDI-TOF-measurements were of no assistance in establishing the identity of the photoproducts from 5a and 5b, we irradiated the iron(II) complex 6b in acetonitrile solution with near-UV light  influences the photochemistry of the ligands The MLCT band at λ = 585 nm does not decrease or change its position during irradiation, whilst the bands due to the anthryl moieties in the near UV region decrease. As was the case for the free ligands, regeneration of the anthryl bands was not observed.5a and 5b and their iron(II)-complexes (6a–b) was successful, investigations regarding their photochemistry were unsatisfactory: Apparently, the anthryl moieties do not undergo the desired [4 + 4]-cycloaddition reaction and the photoproducts could not be identified. Further irradiation experiments with the iron(II)-complex 6b showed that the coordination properties of the terpyridine are not influenced by the photochemistry of the anthryl residues. Hence, the reported anthracene functionalized terpyridines do not appear to be suitable building blocks for photochromic supramolecular structures.Whilst the synthesis of the target molecules A possible explanation for the observed irreversible photoreaction may be an unsymmetrical [4 + 4]-cycloaddition, connecting the anthracene moieties via the 1,4:9′,10′- instead of the 9,10:9′,10′-positions. The line-shape and the absorption increase for λ > 320 nm during irradiation see  is indicGeneral: 4-tert-Butylbenzaldehyde (2) and anthracen-9-ylmethanol (4a) are commercially available and were used as supplied. Methyl 2-acetylisonicotinate (1) +; HRMS: calc. for [C57H43N3O4]+:834.33263; found: 834.33389.833 mg (4.0 mmol) Anthracen-9-ylmethanol (4b) and 590 mg (2.3 mmol) 2-chloro-N-methylpyridinium iodide were added to a solution of 350 mg (772 μmol) 4′-(4-tert-butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-biscarboxylic acid (3) in 20 mL methylene chloride at rt. Subsequently, a solution of 0.35 mL (2.5 mmol) triethylamine in 10 mL methylene chloride was added dropwise, the mixture stirred at rt for 24 h and then poured into 50 mL hydrochloric acid (1 M). The layers were separated, the organic layer washed with 50 mL hydrochloric acid (1 M), dried over MgSO4 and filtered. After removal of the solvent under reduced pressure, an orange solid remained which was purified by column chromatography  to yield 517 mg  of 4′-(4-tert-butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-bis(2-(anthracen-9-yloxy)ethyl)carboxylate (5b) as a pale yellow solid. 1H NMR : 1.42 , 4.43 , 4.48 , 7.23 , 7.30 , 7.64 , 7.82 , 7.88 , 7.93 , 8.10 , 8.37 , 8.92 , 8.96 , 9.15 ; 13C NMR : 31.6 (-C(CH3)3), 35.4 (-C(CH3)3), 65.9 (-CO2CH2-), 73.9 (-CH2-O-ArA), 119.7 , 121.5 , 123.0 , 123.2 (Anth10), 123.7 , 125.6 , 126.1 , 127.0 , 127.7 , 129.1 , 133.4 , 136.4 (tpy4′), 139.2 , 150.8 , 151.3 (Ph1), 151.6 (Anth9), 153.3 (Ph4), 156.3 , 157.9 , 165.1 (-CO2CH2-); ESI-MS : 894 [M]+; HRMS: calc. for [C59H47N3O6]+: 894.35376; found: 894.35203.736 mg (3.1 mmol) 2-(Anthracen-9-yloxy)ethanol (tert-Butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-bis(anthracen-9-ylmethyl)carboxylate (5a) suspended in 20 mL methanol and subsequently treated with a solution of 18 mg (90 μmol) iron(II)chloride tetrahydrate in 10 mL methanol. The mixture was stirred for 6 h at rt. The color changed to deep blue after several minutes. 200 mg (1.23 mmol) Ammonium hexafluorophosphate was added and the mixture stirred for a further 30 min. The blue precipitate was collected by centrifugation and purified by column chromatography . After removal of the solvent, a dark blue solid remained which was characterized as bis-(4′-(4-tert-butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-bis(anthracen-9-ylmethyl)-carboxylate)-iron(II)-hexafluorophosphate (6a). Yield: 153 mg . 1H NMR : 1.44 , 6.35 , 7.07 , 7.24 , 7.49-7.54 , 7.74 , 8.08 , 8.35 , 8.62 , 8.84 , 9.10 ; ESI-MS : 191.1 [AnthCH2]+, 861.7 [M-2 PF6]2+, 1341.4 [M-2 PF6-2 AnthCH]+, 1532.5 [M-2 PF6-AnthCH]+; HRMS: calc. for [C114H86FeN6O8]2+ ([Fe(5a)2]): 860.29462; found: 860.29320.150 mg (180 μmol) 4′-(4-tert-Butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-bis(2-(anthracen-9-yloxy)ethyl)carboxylate (5b) suspended in 30 mL methanol and subsequently treated with a solution of 22 mg (112 μmol) iron(II)chloride tetrahydrate in 15 mL methanol. The mixture was stirred for 6 h at rt. The color changed to deep blue after several minutes. 200 mg (1.23 mmol) Ammonium hexafluorophosphate was added and the mixture stirred for a further 30 min. The blue precipitate was collected by centrifugation and purified by column chromatography . After removal of the solvent, a dark blue solid remained which was characterized as bis-(4′-(4-tert-butylphenyl)-2,2′:6′,2″-terpyridine-4,4″-bis(2-(anthracen-9-yloxy)ethyl)-carboxylate)-iron(II)-hexafluorophosphate (6b). Yield: 196 mg . 1H NMR : 1.57 , 4.64 , 4.81 , 7.13 , 7.21 , 7.42 , 7.49 , 7.73 , 7.88 , 8.07 , 8.21-8.25 , 8.67 , 9.13 . ESI-MS : 921.8 [M-2 PF6]2+, 1988 [M-PF6]+; HRMS: calc. for [C118H94FeN6O12]2+ ([Fe(5b)2]2+): 920.31575; found: 920.31550.200 mg (224 μmol) 4′- and 13C NMR spectra of the organic precursors .Supporting information contains File 11H NMR spectra of compounds 3, 5a–b, 6a–b, and 13C NMR spectra of the organic precursors 3, 5a–b