TY - JOUR A1 - Gonzalez-Chavarria, Ivan A1 - Duprat, Felix A1 - Roa, Francisco J. A1 - Jara, Nery A1 - Toledo, Jorge R. A1 - Miranda, Felipe A1 - Becerra, Jose A1 - Inostroza, Alejandro A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Heydenreich, Matthias A1 - Paz, Cristian T1 - Maytenus disticha extract and an isolated β-Dihydroagarofuran induce mitochondrial depolarization and apoptosis in human cancer cells by increasing mitochondrial reactive oxygen species JF - Biomolecules N2 - Maytenus disticha (Hook F.), belonging to the Celastraceae family, is an evergreen shrub, native of the central southern mountains of Chile. Previous studies demonstrated that the total extract of M. disticha (MD) has an acetylcholinesterase inhibitory activity along with growth regulatory and insecticidal activities. beta-Dihydroagarofurans sesquiterpenes are the most active components in the plant. However, its activity in cancer has not been analyzed yet. Here, we demonstrate that MD has a cytotoxic activity on breast (MCF-7), lung (PC9), and prostate (C4-2B) human cancer cells with an IC50 (mu g/mL) of 40, 4.7, and 5 mu g/mL, respectively, an increasing Bax/Bcl2 ratio, and inducing a mitochondrial membrane depolarization. The beta-dihydroagarofuran-type sesquiterpene (MD-6), dihydromyricetin (MD-9), and dihydromyricetin-3-O-beta-glucoside (MD-10) were isolated as the major compounds from MD extracts. From these compounds, only MD-6 showed cytotoxic activity on MCF-7, PC9, and C4-2B with an IC50 of 31.02, 17.58, and 42.19 mu M, respectively. Furthermore, the MD-6 increases cell ROS generation, and MD and MD-6 induce a mitochondrial superoxide generation and apoptosis on MCF-7, PC9, and C4-2B, which suggests that the cytotoxic effect of MD is mediated in part by the beta-dihydroagarofuran-type that induces apoptosis by a mitochondrial dysfunction. KW - Maytenus disticha KW - beta-dihydroagarofuran-type sesquiterpene KW - dihydromyricetin KW - dihydromyricetin-3-O-beta-glucoside KW - cytotoxic KW - activity KW - Mitochondrial ROS Y1 - 2020 U6 - https://doi.org/10.3390/biom10030377 SN - 2218-273X VL - 10 IS - 3 PB - MDPI CY - Basel ER - TY - JOUR A1 - Krüger, Tobias A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Linker, Torsten T1 - Simple Synthesis of gamma-Spirolactams by Birch Reduction of Benzoic Acids JF - European journal of organic chemistry N2 - A convenient synthesis of gamma-spirolactams in only two steps was developed. Birch reduction of benzoic acids and immediate alkylation with chloroacetonitrile afforded cyclohexadienes in high yields. The products could be isolated by crystallization on a large scale in analytically pure form. Subsequent hydrogenation with platinum(IV) oxide as the catalyst reduced the nitrile functionality and the double bonds in the same step with excellent stereoselectivity. The relative configurations were determined unequivocally by X-ray analyses. Direct cyclization of the intermediary formed amino acids afforded the desired gamma-spirolactams in excellent overall yields. The procedure is characterized by few steps, cheap reagents, and can be performed on a large scale, interesting for industrial processes. KW - Diastereoselectivity KW - Hydrogenation KW - Lactams KW - Reduction KW - Synthetic methods Y1 - 2016 U6 - https://doi.org/10.1002/ejoc.201601650 SN - 1434-193X SN - 1099-0690 IS - 6 SP - 1074 EP - 1077 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Lee, Hui-Chun A1 - Hwang, Jongkook A1 - Schilde, Uwe A1 - Antonietti, Markus A1 - Matyjaszewski, Krzysztof A1 - Schmidt, Bernhard V. K. J. T1 - Toward ultimate control of radical polymerization BT - functionalized metal-organic frameworks as a robust environment for Metal-Catalyzed Polymerizations JF - Chemistry of materials : a publication of the American Chemical Society N2 - Herein, an approach via combination of confined porous textures and reversible deactivation radical polymerization techniques is proposed to advance synthetic polymer chemistry, i.e., a connection of metal-organic frameworks (MOFs) and activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP). Zn-2(benzene-1,4-dicarboxylate)2(1,4-diazabicyclo[2.2.2]-octane) [Zn-2(bdc)(2)(dabco)] is utilized as a reaction environment for polymerization of various methacrylate monomers (methyl, ethyl, benzyl, and isobornyl methacrylate) in a confined nanochannel, resulting in polymers with control over dispersity, end functionalities, and tacticity with respect to distinct molecular size. To refine and reconsolidate the compartmentation effect on polymer regularity, initiator-functionalized Zn MOF was synthesized via cocrystallization with an initiator-functionalized ligand, 2-(2-bromo-2-methylpropanamido)-1,4-benzenedicarboxylate (Brbdc), in different ratios (10%, 20%, and 50%). Through the embedded initiator, surface-initiated ARGET ATRP was directly initiated from the walls of the nanochannels. The obtained polymers had a high molecular weight up to 392 000. Moreover, a significant improvement in end-group functionality and stereocontrol was observed, entailing polymers with obvious increments in isotacticity. The results highlight a combination of MOFs and ATRP that is a promising and universal methodology to prepare various polymers with high molecular weight exhibiting well-defined uniformity in chain length and microstructure as well as the preserved chain-end functionality. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b00546 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 9 SP - 2983 EP - 2994 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Sardarian, Ali Reza A1 - Inaloo, Iman Dindarloo A1 - Modarresi-Alam, Ali Reza A1 - Kleinpeter, Erich A1 - Schilde, Uwe T1 - Metal-Free Regioselective Monocyanation of Hydroxy-, Alkoxy-, and Benzyloxyarenes by Potassium Thiocyanate and Silica Sulfuric Acid as a Cyanating Agent JF - The journal of organic chemistry N2 - A novel and efficient metal- and solvent-free regioselective para-C-H cyanation of hydroxy-, alkoxy-, and benzyloxyarene derivatives has been introduced, using nontoxic potassium thiocyanate as a cyanating reagent in the presence of silica sulfuric acid (SSA). The desired products are obtained in good to high yields without any toxic byproducts. Y1 - 2019 U6 - https://doi.org/10.1021/acs.joc.8b02191 SN - 0022-3263 VL - 84 IS - 4 SP - 1748 EP - 1756 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Alrefai, Anas A1 - Mondal, Suvendu Sekhar A1 - Wruck, Alexander A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Brandt, Philipp A1 - Janiak, Christoph A1 - Schoenfeld, Sophie A1 - Weber, Birgit A1 - Rybakowski, Lawrence A1 - Herrman, Carmen A1 - Brennenstuhl, Katlen A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Behrens, Karsten A1 - Günter, Christina A1 - Müller, Holger A1 - Holdt, Hans-Jürgen T1 - Hydrogen-bonded supramolecular metal-imidazolate frameworks: gas sorption, magnetic and UV/Vis spectroscopic properties JF - Journal of Inclusion Phenomena and Macrocyclic Chemistry N2 - By varying reaction parameters for the syntheses of the hydrogen-bonded metal-imidazolate frameworks (HIF) HIF-1 and HIF-2 (featuring 14 Zn and 14 Co atoms, respectively) to increase their yields and crystallinity, we found that HIF-1 is generated in two different frameworks, named as HIF-1a and HIF-1b. HIF-1b is isostructural to HIF-2. We determined the gas sorption and magnetic properties of HIF-2. In comparison to HIF-1a (Brunauer-Emmett-Teller (BET) surface area of 471m(2) g(-1)), HIF-2 possesses overall very low gas sorption uptake capacities [BET(CO2) surface area=85m(2) g(-1)]. Variable temperature magnetic susceptibility measurement of HIF-2 showed antiferromagnetic exchange interactions between the cobalt(II) high-spin centres at lower temperature. Theoretical analysis by density functional theory confirmed this finding. The UV/Vis-reflection spectra of HIF-1 (mixture of HIF-1a and b), HIF-2 and HIF-3 (with 14 Cd atoms) were measured and showed a characteristic absorption band centered at 340nm, which was indicative for differences in the imidazolate framework. KW - Gas-sorption KW - Ligand design KW - Magnetic properties KW - Supramolecular chemistry KW - Solvothermal synthesis Y1 - 2019 U6 - https://doi.org/10.1007/s10847-019-00926-6 SN - 1388-3127 SN - 1573-1111 VL - 94 IS - 3-4 SP - 155 EP - 165 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Movahedifar, Fahimeh A1 - Modarresi-Alam, Ali Reza A1 - Kleinpeter, Erich A1 - Schilde, Uwe T1 - Dynamic H-1-NMR study of unusually high barrier to rotation about the partial C-N double bond in N,N-dimethyl carbamoyl 5-aryloxytetrazoles JF - Journal of molecular structure N2 - The synthesis of new N,N-dimethyl carbamoyl 5-aryloxytetrazoles have been reported. Their dynamic H-1-NMR via rotation about C-N bonds in moiety of urea group [a; CO-NMe2 and b; (2-tetrazolyl)N-CO rotations] in the solvents CDCl3 (223-333 K) and DMSO (298-363 K) is studied. Accordingly, the free energies of activation, obtained 16.5 and 16.9 kcal mol(-1) respectively, attributed to the conformational isomerization about the Me2N-C=O bond (a rotation). Moreover, a and b barrier to rotations in 5-((4-methylphenoxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide (P) also were computed at level of B3LYP using 6-311++G** basis set. The optimized geometry parameters are in good agreement with X-ray structure data. The computation of energy barrier for a and b was determined 16.9 and 2.5 kcal mol(-1), respectively. The former is completely in agreement with the result obtained via dynamic NMR. X-ray structure analysis data demonstrate that just 2-acylated tetrazole was formed in the case of 5-(p-tolyloxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide. X-ray data also revealed a planar trigonal orientation of the Me2N group which is coplanar to carbonyl group with the partial double-bond C-N character. It also demonstrates the synperiplanar position of C=O group with tetrazolyl ring. On average, in solution the plane containing carbonyl bond is almost perpendicular to the plane of the tetrazolyl ring (because of steric effects as confirmed by B3LY12/6-311++G**) while the plane containing Me2N group is coplanar with carbonyl bond which is in contrast with similar urea derivatives and it demonstrates the unusually high rotational energy barrier of these compounds. (C) 2016 Elsevier B.V. All rights reserved. KW - Dynamic H-1-NMR KW - Carbamoyl tetrazoles KW - Barrier to rotation about C-N bond KW - pi-Stacking KW - B3LYP/6-311++G** Y1 - 2017 U6 - https://doi.org/10.1016/j.molstruc.2016.12.010 SN - 0022-2860 SN - 1872-8014 VL - 1133 SP - 244 EP - 252 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Grunwald, Nicolas A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen A1 - Schilde, Uwe T1 - The crystal structure of 1,1′-bisisoquinoline, C18H12N2 JF - Zeitschrift für Kristallographie : international journal for structural, physical and chemical aspects of crystalline materials ; New crystal structures N2 - C18H12N2, tetragonal, I4(1)/a (no. 88), a = 13.8885(6) angstrom, c = 13.6718(6) angstrom, V = 2637.2(3) angstrom(3), Z = 8, R-gt(F) = 0.0295, wR(ref)(F-2) = 0.0854, T = 210 K. Y1 - 2017 U6 - https://doi.org/10.1515/ncrs-2017-0088 SN - 1433-7266 VL - 232 SP - 839 EP - 841 PB - De Gruyter CY - Berlin ER - TY - JOUR A1 - Mondal, Suvendu Sekhar A1 - Hovestadt, Maximilian A1 - Dey, Subarna A1 - Paula, Carolin A1 - Glomb, Sebastian A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Janiak, Christoph A1 - Hartmann, Martin A1 - Holdt, Hans-Jürgen T1 - Synthesis of a partially fluorinated ZIF-8 analog for ethane/ethene separation JF - CrystEngComm N2 - The separation of ethane/ethene mixtures (as well as other paraffin/olefin mixtures) is one of the most important but challenging processes in the petrochemical industry. In this work, we report the synthesis of ZIF-318, isostructural to ZIF-8 but built from the mixed linkers of 2-methylimidazole (L1) and 2-trifluoromethylimidazole (L2) (ZIF-318 = [(Zn(L1)(L2)](n)). The synthesis has been optimized to proceed without ZnO-formation. Using only the L2 linker under solvothermal conditions afforded ZnO-embedded in the H-bonded and non-porous coordination polymer ZnO@[Zn-2(L2)(2)(HCOO)(OH)](n). The slight differences in the size of the substituents (-CH3 vs. -CF3) possibly in combination with different electronic inductive effects led to small but significant changes to the pore size and properties respectively, though the effective pore opening (aperture) size of ZIF-318 remained the same in comparison with ZIF-8. ZIF-318 is chemically (boiling water, methanol, benzene, and wide pH range at room temperature for 1 day), thermally (up to 310 degrees C) stable, and more hydrophobic than ZIF-8 which is proven by contact angle measurement. ZIF-318 can be activated for N-2, CO2, CH4, H-2, ethane, ethane, propane, and propene gases sorptions. Consequently, in breakthrough experiments, the ethane/ethene mixtures can be separated. Y1 - 2017 U6 - https://doi.org/10.1039/c7ce01438d SN - 1466-8033 VL - 19 SP - 5882 EP - 5891 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Abouserie, Ahed A1 - Zehbe, Kerstin A1 - Metzner, Philipp A1 - Kelling, Alexandra A1 - Günter, Christina A1 - Schilde, Uwe A1 - Strauch, Peter A1 - Körzdörfer, Thomas A1 - Taubert, Andreas T1 - Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry. KW - Ionic liquids KW - Alkylpyridinium salts KW - Structure elucidation KW - Phase transitions Y1 - 2017 U6 - https://doi.org/10.1002/ejic.201700826 SN - 1434-1948 SN - 1099-0682 SP - 5640 EP - 5649 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Abouserie, Ahed A1 - Zehbe, Kerstin A1 - Metzner, Philipp A1 - Kelling, Alexandra A1 - Günter, Christina A1 - Schilde, Uwe A1 - Strauch, Peter A1 - Körzdörfer, Thomas A1 - Taubert, Andreas T1 - Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry. KW - Ionic liquids KW - Alkylpyridinium salts KW - Structure elucidation KW - Phase transitions Y1 - 2017 U6 - https://doi.org/10.1002/ejic.201700826 SN - 1434-1948 SN - 1099-0682 SP - 5640 EP - 5649 PB - Wiley-VCH CY - Weinheim ER -