TY - JOUR A1 - Pimpalpalle, Tukaram M. A1 - Yin, Jian A1 - Linker, Torsten T1 - Barton radical reactions of 2-C-branched carbohydrates JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - Barton esters have been introduced into the side chain of carbohydrates with high yields in only a few steps from easily available glycals. Their radical reactions afford 2-C-methyl and 2-C-bromomethyl hexoses, pentoses and disaccharides in good yields in analytically pure form. Since the Barton esters have been synthesized by an oxidative radical addition and their transformations by reductive radical processes, our results demonstrate the power of such reactions in carbohydrate chemistry. Y1 - 2012 U6 - https://doi.org/10.1039/c1ob06370g SN - 1477-0520 VL - 10 IS - 1 SP - 103 EP - 109 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Hildebrandt, Niko A1 - Geissler, Daniel ED - Zahavy, E ED - Ordentlich, A ED - Yitzhaki, S ED - Shafferman, A T1 - Semiconductor quantum dots as FRET acceptors for multiplexed diagnostics and molecular ruler application JF - Advances in Experimental Medicine and Biology N2 - Applications based on Forster resonance energy transfer (FRET) play an important role for the determination of concentrations and distances within nanometer-scale systems in vitro and in vivo in many fields of biotechnology. Semiconductor nanocrystals (Quantum dots - QDs) possess ideal properties for their application as FRET acceptors when the donors have long excited state lifetimes and when direct excitation of QDs can be efficiently suppressed. Therefore, luminescent terbium complexes (LTCs) with excited state lifetimes of more than 2 ms are ideal FRET donor candidates for QD-acceptors. This chapter will give a short overview of theoretical and practical background of FRET, QDs and LTCs, and present some recent applications of LTC-QD FRET pairs for multiplexed ultra-sensitive in vitro diagnostics and nanometer-resolution molecular distance measurements. KW - Diagnostics KW - FRET KW - Imaging KW - Quantum dots KW - Terbium Y1 - 2012 SN - 978-94-007-2554-6 SN - 978-94-007-2555-3 U6 - https://doi.org/10.1007/978-94-007-2555-3_8 SN - 0065-2598 VL - 733 SP - 75 EP - 86 PB - Springer CY - Dordrecht ER - TY - JOUR A1 - Herfurth, Christoph A1 - Voll, Dominik A1 - Buller, Jens A1 - Weiss, Jan A1 - Barner-Kowollik, Christopher A1 - Laschewsky, André T1 - Radical addition fragmentation chain transfer (RAFT) polymerization of ferrocenyl (meth)acrylates JF - Journal of polymer science : A, Polymer chemistry N2 - We report on the controlled free radical homopolymerization of 1-ferrocenylethyl acrylate as well as of three new ferrocene bearing monomers, namely 4-ferrocenylbutyl acrylate, 2-ferrocenylamido-2-methylpropyl acrylate, and 4-ferrocenylbutyl methacrylate, by the RAFT technique. For comparison, the latter monomer was polymerized using ATRP, too. The ferrocene containing monomers were found to be less reactive than their analogues free of ferrocene. The reasons for the low polymerizability are not entirely clear. As the addition of free ferrocene to the reaction mixture did not notably affect the polymerizations, sterical hindrance by the bulky ferrocene moiety fixed on the monomers seems to be the most probable explanation. Molar masses found for 1-ferrocenylethyl acrylate did not exceed 10,000 g mol(-1), while for 4-ferrocenylbutyl (meth) acrylate molar masses of 15,000 g mol(-1) could be obtained. With PDIs as low as 1.3 in RAFT polymerization of the monomers, good control over the polymerization was achieved. KW - ferrocene KW - living radical polymerization (LRP) KW - monomers KW - radical addition fragmentation chain transfer (RAFT) KW - radical polymerization KW - redox polymers KW - synthesis Y1 - 2012 U6 - https://doi.org/10.1002/pola.24994 SN - 0887-624X VL - 50 IS - 1 SP - 108 EP - 118 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Schwadtke, Ulrike A1 - Schmuecker, Simon A1 - Schaefer, Philipp A1 - Kuckling, Dirk A1 - Beuermann, Sabine T1 - Alkyne-azide coupling of tailored poly(vinylidene fluoride) and polystyrene for the synthesis of block copolymers JF - Polymer Chemistry N2 - The synthesis of block copolymers consisting of poly(vinylidene fluoride) (PVDF) and polystyrene (PS) is reported. Firstly, a propargyl-functionalized alkoxyamine initiator (PgOTIPNO) was prepared and subsequently used for the preparation of a propargyl-terminated PS homopolymer of different chain lengths with low dispersities via nitroxide-mediated radical polymerization. A tailored PVDF homopolymer with iodine end groups originating from iodine transfer polymerization was transformed to PVDF with azide end group. Then, alkyne-terminated PS with different molecular weights and azide-terminated PVDF were joined together via copper-catalyzed alkyne-azide coupling. The block copolymers were characterized using H-1-NMR, F-19-NMR, IR, SEC, and DSC. Y1 - 2012 U6 - https://doi.org/10.1039/c1py00427a SN - 1759-9954 VL - 3 IS - 2 SP - 409 EP - 414 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Weiss, Jan A1 - Li, Ang A1 - Wischerhoff, Erik A1 - Laschewsky, André T1 - Water-soluble random and alternating copolymers of styrene monomers with adjustable lower critical solution temperature JF - Polymer Chemistry N2 - Random copolymers of 4-vinylbenzyl tri(oxyethylene) and tetra(oxyethylene) ethers, as well as alternating copolymers of 4-vinylbenzyl methoxytetra(oxyethylene) ether and a series of N-substituted maleimides, were synthesised by conventional free radical polymerisation, reversible addition fragmentation chain transfer (RAFT) and atom transfer radical polymerisation (ATRP). Their thermosensitive behaviour in aqueous solution was studied by turbidimetry and dynamic light scattering. Depending on the copolymer composition, a LCST type phase transition was observed in water. The transition temperature of the obtained random as well as alternating copolymers could be varied within a broad temperature window. In the case of the random copolymers, transition temperatures could be easily fine-tuned, as they showed a linear dependence on the copolymer composition, and were additionally modified by the nature of the polymer end-groups. Alternating copolymers were extremely versatile for implementing a broad range of variations of the phase transition temperatures. Further, while alternating copolymers derived from 4-vinylbenzyl methoxytetra(oxyethylene) ether and maleimides with small hydrophobic side chains underwent macroscopic phase separation when dissolved in water and heated above their cloud point, the incorporation of maleimides bearing larger hydrophobic substituents resulted in the formation of mesoglobules above the phase transition temperature, with hydrodynamic diameters of less than 100 nm. Y1 - 2012 U6 - https://doi.org/10.1039/c1py00422k SN - 1759-9954 VL - 3 IS - 2 SP - 352 EP - 361 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Lippold, Holger A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Lippmann-Pipke, Johanna T1 - Diffusion, degradation or on-site stabilisation - identifying causes of kinetic processes involved in metal-humate complexation JF - Applied geochemistry : journal of the International Association of Geochemistry and Cosmochemistry N2 - The applicability of equilibrium models for humic-bound transport of toxic or radioactive metals is affected by kinetic processes leading to an increasing inertness of metal-humic complexes. The chemical background is not yet understood. It is widely believed that bound metals undergo an in-diffusion process within the humic colloids, changing from weaker to stronger binding sites. This work is focussed on the competition effect of Al(III) on complexation of Tb(III) or Eu(III) as analogues of trivalent actinides. By using ion exchange and spectroscopic methods, their bound fractions were determined for solutions of Al and humic acid that had been pre-equilibrated for different periods of time. Whilst the amount of bound Al remained unchanged, its blocking effect was found to increase over a time frame of 2 days, which corresponds to the kinetics of the increase in complex inertness reported in most pertinent studies. Thus, the derived "diffusion theory'' turned out to be inapplicable, since it cannot explain an increase in competition for the "initial'' sites. A delayed degradation of polynuclear species (as found for Fe) does not occur. Consequently, the temporal changes must be based on structural rearrangements in the vicinity of bound Al, complicating the exchange or access. Time-dependent studies by laser fluorescence spectroscopy (steady-state and time-resolved) yielded evidence of substantial alterations, which were, however, immediately induced and did not show any significant trend on the time scale of interest, suggesting that the stabilisation process is based on comparatively moderate changes. Y1 - 2012 U6 - https://doi.org/10.1016/j.apgeochem.2011.11.001 SN - 0883-2927 VL - 27 IS - 1 SP - 250 EP - 256 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Suslova, Elena N. A1 - Kleinpeter, Erich T1 - Conformational analysis of 4,4-dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)-1,4,2,6-oxazadisilinane JF - Journal of physical organic chemistry N2 - 4,4-Dimethyl-1-(trifluoromethylsulfonyl)-1,4-azasilinane 1 and 2,2,6,6-tetramethyl-4-(trifluoromethylsulfonyl)-1,4,2,6-oxazadisilinane 2 were studied by variable temperature dynamic 1H, 13C, 19F NMR spectroscopy and theoretical calculations at the DFT (density functional theory) and MP2 (Moller-Plesset 2) levels of theory. Both kinetic (barriers to ring inversion) and thermodynamic data (frozen conformational equilibria) could be obtained for the two compounds. The computations revealed two minima on the potential energy surface for molecules 1 and 2 corresponding to the rotamers with the CF3SO2 group directed inward and outward the ring, the latter being 0.20.4 kcal/mol (for 1) and 1.1 kcal/mol (for 2) more stable than the former. The vibrational calculations at the DFT and MP2 levels of theory give the values of the free energy difference Delta G degrees for the 'inward' reversible arrow 'outward' equilibrium consistent with those determined from the experimentally measured ratio of the rotamers. The structure of crystalline compound 2 was ascertained by X-ray diffraction analysis. KW - conformational analysis KW - dynamic NMR KW - quantum chemical calculations KW - 2 KW - 6-disilamorpholines KW - 4-silapiperidines Y1 - 2012 U6 - https://doi.org/10.1002/poc.1882 SN - 0894-3230 VL - 25 IS - 1 SP - 83 EP - 90 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Baranac-Stojanovic, Marija A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - Is the conventional interpretation of the anisotropic effects of C=C double bonds and aromatic rings in NMR spectra in terms of the p-electron shielding/deshielding contributions correct? JF - Chemistry - a European journal N2 - Based on the nucleus-independent chemical shift (NICS) concept, isotropic magnetic shielding values have been computed along the three Cartesian axes for ethene, cyclobutadiene, benzene, naphthalene, and benzocyclobutadiene, starting from the molecular/ring center up to 10 angstrom away. These through-space NMR spectroscopic shielding (TSNMRS) values, which reflect the anisotropic effects, have been broken down into contributions from localized- and canonical molecular orbitals (LMOs and CMOs); these contributions revealed that the proton NMR spectroscopic chemical shifts of nuclei that are spatially close to the C?C double bond or the aromatic ring should not be explained in terms of the conventionally accepted p-electron shielding/deshielding effects. In fact, these effects followed the predictions only for the antiaromatic cyclobutadiene ring. KW - ab initio calculations KW - anisotropic effects KW - NMR spectroscopy KW - nucleus-independent chemical shift KW - pi interactions Y1 - 2012 U6 - https://doi.org/10.1002/chem.201101882 SN - 0947-6539 VL - 18 IS - 1 SP - 370 EP - 376 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Mickler, Wulfhard A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen T1 - Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono-and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF6)(2), [1] (PF6)(2)-[5](PF6)(2), and [{Ru(L-L)(2)}(2)(mu-tape)](PF6)(4), [6](PF6)(4)-[10](PF6)(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4' 5,5'-tetramethyl-2,2'- bipyridine)}, respectively, were synthesized. The X-ray structures of tape center dot 2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF6)(2)center dot 0.5CH(3)CN center dot 0.5toluene, [Ru(dmbpy)(2)(tape)] (PF6)(2)center dot 2toluene and [Ru(dtbbpy)(2)(tape)](PF6)(2) center dot 3acetone center dot 0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido [3,2-a:2',3'-c:3 '',2''-h:2''',3'''-j] phenazin (tpphz) species. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt11805j SN - 1477-9226 VL - 41 IS - 9 SP - 2788 EP - 2797 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Balci, Kubilay A1 - Yapar, G. A1 - Akkaya, Y. A1 - Akyuz, S. A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - A conformational analysis and vibrational spectroscopic investigation on 1,2-bis(o-carboxyphenoxy) ethane molecule JF - Vibrational spectroscopy : an international journal devoted to applications of infrared and raman spectroscopy N2 - The minima on the potential energy surface of 1,2-bis(o-carboxyphenoxy)ethane (CPE) molecule in its electronic ground state were searched by a molecular dynamics simulation performed with MM2 force field. For each of the found minimum-energy conformers, the corresponding equilibrium geometry, charge distribution, HOMO-LUMO energy gap, force field, vibrational normal modes and associated IR and Raman spectral data were determined by means of the density functional theory (DFT) based electronic structure calculations carried out by using B3LYP method and various Pople-style basis sets. The obtained theoretical data confirmed the significant effects of the intra- and inter-molecular hydrogen bonding interactions on the conformational structure, force field, and group vibrations of the molecule. The same data have also revealed that two of the determined stable conformers, both of which exhibit pseudo-crown structure, are considerably more favorable in energy to the others and accordingly provide the major contribution to the experimental spectra of CPE. In the light of the improved vibrational spectral data obtained within the "SQM FF" methodology and "Dual Scale Factors" approach for the monomer and dimer forms of these two conformers, a reliable assignment of the fundamental bands observed in the experimental room-temperature IR and Raman spectra of the molecule was given, and the sensitivities of its group vibrations to conformation, substitution and dimerization were discussed. KW - Glycol podands KW - Salicylic acid KW - IR and Raman spectra KW - SQM FF KW - Dual Scale Factors Y1 - 2012 U6 - https://doi.org/10.1016/j.vibspec.2011.11.011 SN - 0924-2031 VL - 58 IS - 1-2 SP - 27 EP - 43 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Yin, Jian A1 - Linker, Torsten T1 - Recent advances in the stereoselective synthesis of carbohydrate 2-C-analogs JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - C-branched carbohydrates are of current interest for glycochemistry, are widely found in nature and serve as important subunits in many antibiotics, bacterial polysaccharides and macrolides. Among C-functionalized saccharides, 2-C-branched carbohydrates represent challenging structures for synthetic chemists, since in contrast to C-glycosides they are not easily accessible from glycosyl bromides or other simple precursors. In this perspective we want to summarize recent approaches to 2-C-branched carbohydrates over the past fifteen years. The two main strategies are based on ring-opening of 1,2-cyclopropanated carbohydrates by various reagents, as well as radical additions to glycals and further transformations, developed in our group. Both methods are characterized by high stereoselectivities and good yields and give access to a broad variety of functionalized carbohydrate 2-C-analogs. Y1 - 2012 U6 - https://doi.org/10.1039/c2ob06529k SN - 1477-0520 VL - 10 IS - 12 SP - 2351 EP - 2362 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Xie, Zai-Lai A1 - Xu, Hai-Bing A1 - Gessner, Andre A1 - Kumke, Michael Uwe A1 - Priebe, Magdalena A1 - Fromm, Katharina M. A1 - Taubert, Andreas T1 - A transparent, flexible, ion conductive, and luminescent PMMA ionogel based on a Pt/Eu bimetallic complex and the ionic liquid [Bmim][N(Tf)(2)] JF - Journal of materials chemistry N2 - Transparent, ion-conducting, luminescent, and flexible ionogels based on the room temperature ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl) imide [Bmim][N(Tf)(2)], a PtEu2 chromophore, and poly(methylmethacrylate) (PMMA) have been prepared. The thermal stability of the PMMA significantly increases with IL incorporation. In particular, the onset weight loss observed at ca. 229 degrees C for pure PMMA increases to 305 degrees C with IL addition. The ionogel has a high ionic conductivity of 10(-3) S cm(-1) at 373 K and exhibits a strong emission in the red with a long average luminescence decay time of tau = 890 mu s. The resulting material is a new type of soft hybrid material featuring useful thermal, optical, and ion transport properties. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm15862k SN - 0959-9428 VL - 22 IS - 16 SP - 8110 EP - 8116 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Koeth, Anja A1 - Tiersch, Brigitte A1 - Appelhans, Dietmar A1 - Gradzielski, Michael A1 - Cölfen, Helmut A1 - Koetz, Joachim T1 - Synthesis of Core-Shell Gold Nanoparticles with Maltose-Modified Poly(Ethyleneimine) JF - Journal of dispersion science and technology N2 - The synthesis of ultrafine gold nanoparticles in presence of maltose-modified hyperbranched poly(ethyleneimines) (PEI) is described. The polymer acted as both a reducing and stabilising agent in the particle formation process. The nanoparticles were characterized by means of dynamic light scattering (DLS), transmission electron microscopy (TEM), analytical ultracentrifugation (AUC), small-angle x-ray scattering (SAXS), and small-angle neutron scattering (SANS). The mechanism of nanoparticle formation can be described in two steps. The reduction process of the Au3+ ions located in the inner coil region of the hyperbranched PEI led to the formation of a compact gold core, and is accompanied by a collapse of the polymer coil. Therefore, in the subsequent reduction process a gold-polymer hybrid shell is formed. By using the PEI of higher molar mass, core-shell gold nanoparticles of about 3.6 nm size with a more narrow size distribution and special fluorescence behavior could be synthesized. KW - Gold nanoparticles KW - gold-polymer hybrid shell KW - maltose-modified poly(ethyleneimine) Y1 - 2012 U6 - https://doi.org/10.1080/01932691.2010.530084 SN - 0193-2691 VL - 33 IS - 1-3 SP - 52 EP - 60 PB - Taylor & Francis Group CY - Philadelphia ER - TY - JOUR A1 - Sumpf, Bernd A1 - Maiwald, Martin A1 - Muller, Andre A1 - Ginolas, Arnim A1 - Haeusler, Karl A1 - Erbert, Goetz A1 - Traenkle, Guenther T1 - Reliable operation for 14 500 h of a wavelength-stabilized Diode Laser System on a Microoptical Bench at 671 nm JF - IEEE transactions on components, packaging and manufacturing technology N2 - Reliability tests for wavelength-stabilized compact diode laser systems emitting at 671 nm are presented. The devices were mounted on microoptical benches with the dimensions of 13 mm x 4 mm. Reflecting Bragg gratings were used for wavelength stabilization and emission width narrowing. The reliability tests were performed at 25 degrees C and at an output power up to 10 mW per micrometer stripe width of the gain medium. Reliable operation could be demonstrated over a test time up to 14 500 h at an output power up to 1.0 W. Environmental tests using random vibrations with acceleration up to 29 g were performed without deterioration of the devices. KW - High-power lasers KW - laser resonators KW - Raman spectroscopy KW - reliability KW - semiconductor lasers Y1 - 2012 U6 - https://doi.org/10.1109/TCPMT.2011.2171342 SN - 2156-3950 VL - 2 IS - 1 SP - 116 EP - 121 PB - Inst. of Electr. and Electronics Engineers CY - Piscataway ER - TY - JOUR A1 - Goebel, Ronald A1 - White, Robin J. A1 - Titirici, Maria-Magdalena A1 - Taubert, Andreas T1 - Carbon-based ionogels tuning the properties of the ionic liquid via carbon-ionic liquid interaction JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The behavior of two ionic liquids (ILs), 1-ethyl-3-methylimidazolium dicyanamide [Emim][DCA] and 1-ethyl-3-methylimidazolium triflate [Emim][TfO], in (meso) porous carbonaceous hosts was investigated. Prior to IL incorporation into the host, the carbon matrix was thermally annealed between 180 and 900 degrees C to control carbon condensation and surface chemistry. The resulting materials have an increasing "graphitic'' carbon character with increasing treatment temperature, reflected in a modified behavior of the ILs when impregnated into the carbon host. The two ILs show significant changes in the thermal behavior as measured from differential scanning calorimetry; these changes can be assigned to anion-pi interaction between the IL anions and the pore wall surfaces of these flexible carbonaceous support materials. Y1 - 2012 U6 - https://doi.org/10.1039/c2cp23929a SN - 1463-9076 VL - 14 IS - 17 SP - 5992 EP - 5997 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Razzaq, Muhammad Yasar A1 - Behl, Marc A1 - Frank, Ute A1 - Koetz, Joachim A1 - Szczerba, Wojciech A1 - Lendlein, Andreas T1 - Oligo(omega-pentadecalactone) decorated magnetic nanoparticles JF - Journal of materials chemistry N2 - Hybrid magnetic nanoparticles (mgNP) with a magnetite core diameter of 10 +/- 1 nm surface functionalized with oligo(omega-pentadecalactone) (OPDL) oligomers with M-n between 1300 and 3300 g mol(-1) could be successfully prepared having OPDL grafted from 200 mg g(-1) to 2170 mg g(-1). The particles are dispersible in chloroform resulting in stable suspensions. Magnetic response against an external magnetic field proved the superparamagnetic nature of the particles with a low coercivity (B-c) value of 297 mu T. The combination of the advantageous superparamagnetism of the mgNP with the exceptional stability of OPDL makes these novel hybrid mgNP promising candidates as multifunctional building blocks for magnetic nanocomposites with tunable physical properties. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm16146j SN - 0959-9428 VL - 22 IS - 18 SP - 9237 EP - 9243 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Neumann, Mike A1 - Noeske, Robert A1 - Taubert, Andreas A1 - Tiersch, Brigitte A1 - Strauch, Peter T1 - Highly structured, biomorphous beta-SiC with high specific surface area from Equisetaceae JF - Journal of materials chemistry N2 - Mesoporous, highly structured silicon carbide (beta-SiC) was synthesised from renewable plant materials (two Equisetaceae species) in a one-step carbothermal process at remarkably low temperatures down to 1200 degrees C. The SiC precursor is a silicon-carbon mixture with finely dispersed carbon prepared by pyrolysis of the organic plant matrix. Yields are 3 to 100% (omega(Si/Si) related to the silicon deposited in the plant material), depending on reaction temperature and time. IR spectroscopy, X-ray diffraction, and nitrogen sorption prove the formation of high-purity beta-SiC with minor inorganic impurities after purification and a high specific surface area of up to 660 m(2) g(-1). Scanning electron microscopy shows that the plant morphology is maintained in the final SiC. Sedimentation analysis finds a mean particle size (diameters d(50)) of 20 mu m. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm30253e SN - 0959-9428 VL - 22 IS - 18 SP - 9046 EP - 9051 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schmidt, Bernd A1 - Elizarov, Nelli T1 - Selective arene functionalization through sequential oxidative and non-oxidative Heck reactions JF - Chemical communications N2 - A sequence of acetamide directed oxidative Heck reaction and deacetylation-diazotation-Heck coupling allows the traceless removal of the acetamide group and its dual exploitation as a catalyst directing group and a leaving group. Y1 - 2012 U6 - https://doi.org/10.1039/c2cc30752a SN - 1359-7345 VL - 48 IS - 36 SP - 4350 EP - 4352 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Zhong, Qi A1 - Metwalli, Ezzeldin A1 - Kaune, Gunar A1 - Rawolle, Monika A1 - Bivigou Koumba, Achille Mayelle A1 - Laschewsky, André A1 - Papadakis, Christine M. A1 - Cubitt, Robert A1 - Müller-Buschbaum, Peter T1 - Switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) probed with in situ neutron reflectivity JF - Soft matter N2 - The switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) (PMDEGA) are investigated. Homogeneous and smooth PMDEGA films with a thickness of 35.9 nm are prepared on silicon substrates by spin coating. As probed with white light interferometry, PMDEGA films with a thickness of 35.9 nm exhibit a phase transition temperature of the lower critical solution temperature (LCST) type of 40 degrees C. In situ neutron reflectivity is performed to investigate the thermo-responsive behavior of these PMDEGA hydrogel films in response to a sudden thermal stimulus in deuterated water vapor atmosphere. The collapse transition proceeds in a complex way which can be seen as three steps. The first step is the shrinkage of the initially swollen film by a release of water. In the second step the thickness remains constant with water molecules embedded in the film. In the third step, perhaps due to a conformational rearrangement of the collapsed PMDEGA chains, water is reabsorbed from the vapor atmosphere, thereby giving rise to a relaxation process. Both the shrinkage and relaxation processes can be described by a simple model of hydrogel deswelling. Y1 - 2012 U6 - https://doi.org/10.1039/c2sm25401h SN - 1744-683X VL - 8 IS - 19 SP - 5241 EP - 5249 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Herfurth, Christoph A1 - de Molina, Paula Malo A1 - Wieland, Christoph A1 - Rogers, Sarah A1 - Gradzielski, Michael A1 - Laschewsky, André T1 - One-step RAFT synthesis of well-defined amphiphilic star polymers and their self-assembly in aqueous solution JF - Polymer Chemistry N2 - Multifunctional chain transfer agents for RAFT polymerisation were designed for the one-step synthesis of amphiphilic star polymers. Thus, hydrophobically end-capped 3- and 4-arm star polymers, as well as linear ones for reference, were made of the hydrophilic monomer N,N-dimethylacrylamide (DMA) in high yield with molar masses up to 150 000 g mol(-1), narrow molar mass distribution (PDI <= 1.2) and high end group functionality (similar to 90%). The associative telechelic polymers form transient networks of interconnected aggregates in aqueous solution, thus acting as efficient viscosity enhancers and rheology modifiers, eventually forming hydrogels. The combination of dynamic light scattering (DLS), small angle neutron scattering (SANS) and rheology experiments revealed that several molecular parameters control the structure and therefore the physical properties of the aggregates. In addition to the size of the hydrophilic block (maximum length for connection) and the length of the hydrophobic alkyl chain ends (stickiness), the number of arms (functionality) proved to be a key parameter. Y1 - 2012 U6 - https://doi.org/10.1039/c2py20126g SN - 1759-9954 VL - 3 IS - 6 SP - 1606 EP - 1617 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Debatin, Franziska A1 - Möllmer, Jens A1 - Mondal, Suvendu Sekhar A1 - Behrens, Karsten A1 - Möller, Andreas A1 - Staudt, Reiner A1 - Thomas, Arne A1 - Holdt, Hans-Jürgen T1 - Mixed gas adsorption of carbon dioxide and methane on a series of isoreticular microporous metal-organic frameworks based on 2-substituted imidazolate-4-amide-5-imidates JF - Journal of materials chemistry N2 - In this work the adsorption of CO2 and CH4 on a series of isoreticular microporous metal-organic frameworks based on 2-substituted imidazolate-4-amide-5-imidates, IFP-1-IFP-6 (IFP Imidazolate Framework Potsdam), is studied firstly by pure gas adsorption at 273 K. All experimental isotherms can be nicely described by using the Toth isotherm model and show the preferred adsorption of CO2 over CH4. At low pressures the Toth isotherm equation exhibits a Henry region, wherefore Henry's law constants for CO2 and CH4 uptake could be determined and ideal selectivity (alpha CO2/CH4) has been calculated. Secondly, selectivities were calculated from mixture data by using nearly equimolar binary mixtures of both gases by a volumetric-chromatographic method to examine the IFPs. Results showed the reliability of the selectivity calculation. Values of (alpha CO2/CH4) around 7.5 for IFP-5 indicate that this material shows much better selectivities than IFP-1, IFP-2, IFP-3, IFP-4 and IFP-6 with slightly lower selectivity (alpha CO2/CH4) = 4-6. The preferred adsorption of CO2 over CH4 especially of IFP-5 and IFP-4 makes these materials suitable for gas separation application. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm15811f SN - 0959-9428 VL - 22 IS - 20 SP - 10221 EP - 10227 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Si, Satyabrata A1 - Taubert, Andreas A1 - Mantion, Alexandre A1 - Rogez, Guillaume A1 - Rabu, Pierre T1 - Peptide-intercalated layered metal hydroxides effect of peptide chain length and side chain functionality on structural, optical and magnetic properties JF - Chemical science N2 - New hybrid materials have been prepared by grafting synthetic peptides in the interlayer spacing of Cu(II) and Co(II) layered simple hydroxides (LSHs). The interlayer spacing of the hybrids depends on the peptide chain length; the dependence is specific for the copper and cobalt-based hybrids. This suggests a metal-or LSH-specific interaction of the peptides with the respective inorganic layers. When tyrosine is present in the peptide, its fluorescence is quenched after grafting the peptide to the LSH. Studies of the luminescence vs. pH indicate deprotonation of the tyrosine moieties to tyrosinate at high pH, accompanied by the onset of luminescence. The luminescence increases with increasing OH- concentration, suggesting an application of the hybrids as chemical sensors. Moreover, the peptides influence the magnetic properties of the hybrids. The copper-based hybrids behave antiferromagnetically and the cobalt-based hybrids are ferrimagnets. Y1 - 2012 U6 - https://doi.org/10.1039/c2sc01087a SN - 2041-6520 VL - 3 IS - 6 SP - 1945 EP - 1957 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Are lithium and sodium salts of N-(2-hydroxyphenyl)-salicylaldimine aromatic metalla-hetero[10]annulenes? An answer given by spatial magnetic properties (through space NMR shieldings-TSNMRS) JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The spatial magnetic properties (through space NMR shieldings-TSNMRS) of the enol tautomer of N-(2-hydroxyphenyl)-salicylaldimine, the lithium and sodium salts in comparison with cyclodecapentaene and pyrano[2,3-b] pyrrole were studied to answer this question. Y1 - 2012 U6 - https://doi.org/10.1039/c2cp40501f SN - 1463-9076 VL - 14 IS - 24 SP - 8742 EP - 8746 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Klaumünzer, Bastian A1 - Kröner, Dominik A1 - Lischka, Hans A1 - Saalfrank, Peter T1 - Non-adiabatic excited state dynamics of riboflavin after photoexcitation JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Flavins are chromophores in light-gated enzymes and therefore central in many photobiological processes. To unravel the optical excitation process as the initial, elementary step towards signal transduction, detailed ultrafast (femtosecond) experiments probing the photo-activation of flavins have been carried out recently [Weigel et al., J. Phys. Chem. B, 2011, 115, 3656-3680.]. The present paper contributes to a further understanding and interpretation of these experiments by studying the post-excitation vibrational dynamics of riboflavin (RF) and microsolvated riboflavin, RF center dot 4H(2)O, using first principles non-adiabatic molecular dynamics. By analyzing the characteristic atom motions and calculating time-resolved stimulated emission spectra following pi pi* excitation, it is found that after optical excitation C-N and C-C vibrations in the isoalloxazine rings of riboflavin set in. The Franck-Condon (vertically excited) state decays within about 10 fs, in agreement with experiment. Anharmonic coupling leads to Intramolecular Vibrational energy Redistribution (IVR) on the timescale of about 80-100 fs, first to (other) C-C stretching modes of the isoalloxazine rings, then by energy spread over the whole molecule, including low-frequency in-plane modes. The IVR is accompanied by a red-shift and broadening of the emission spectrum. When RF is microsolvated with four water molecules, an overall redshift of optical spectra by about 20 nm is observed but the relaxation dynamics is only slightly affected. For several trajectories, a tendency for hydrogen transfer from water to flavin-nitrogen (N-5) was found. Y1 - 2012 U6 - https://doi.org/10.1039/c2cp40978j SN - 1463-9076 VL - 14 IS - 24 SP - 8693 EP - 8702 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schmidt, Bernd A1 - Krehl, Stefan A1 - Jablowski, Eric T1 - Assisted tandem catalytic RCM-aromatization in the synthesis of pyrroles and furans JF - Organic & biomolecular chemistry : an international journal of synthetic, physical and biomolecular organic chemistry N2 - An assisted tandem catalytic transformation of diallyl amines and diallyl ethers into N-aryl pyrroles and furans, respectively, is described. The sequence relies on ring closing metathesis followed by dehydrogenation of the initially formed dihydropyrroles and dihydrofurans. Both steps are Ru-catalyzed, but the sequence requires only one precatalyst, because conversion of the metathesis catalyst into the dehydrogenation catalyst is achieved in situ, triggered by the oxidant tert-butyl hydroperoxide. Y1 - 2012 U6 - https://doi.org/10.1039/c2ob25543j SN - 1477-0520 VL - 10 IS - 26 SP - 5119 EP - 5130 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Vukicevic, Radovan A1 - Vukovic, Ivana A1 - Stoyanov, Hristiyan A1 - Korwitz, Andreas A1 - Pospiech, Doris A1 - Kofod, Guggi A1 - Loos, Katja A1 - ten Brinke, Gerrit A1 - Beuermann, Sabine T1 - Poly(vinylidene fluoride)-functionalized single-walled carbon nanotubes for the preparation of composites with improved conductivity JF - Polymer Chemistry N2 - The surface of single-walled carbon nanotubes (SWCNTs) was functionalized with azide-terminated poly(vinylidene fluoride) (PVDF). Functionalization was confirmed by dispersibility, Raman spectroscopy, and thermogravimetric analyses. Raman spectra show disordering of the SWCNTs, thus, strongly suggesting that PVDF was covalently attached to SWCNTs. Functionalized SWCNTs were mixed with commercially available PVDF in a twin-screw extruder and thin films were obtained by melt-pressing. Films containing 0.5 and 1 wt% PVDF-functionalized SWCNTs exhibited significantly improved electrical conductivity compared to PVDF films containing pristine SWCNTs. Y1 - 2012 U6 - https://doi.org/10.1039/c2py20166f SN - 1759-9954 VL - 3 IS - 8 SP - 2261 EP - 2265 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kammer, Stefan A1 - Starke, Ines A1 - Pietrucha, Andreas A1 - Kelling, Alexandra A1 - Mickler, Wulfhard A1 - Schilde, Uwe A1 - Dosche, Carsten A1 - Kleinpeter, Erich A1 - Holdt, Hans-Jürgen T1 - 1,12-Diazaperylene and 2,11-dialkylated-1,12-diazaperylene iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6: new supramolecular assemblies JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - A series of new monocationic iridium(III) complexes [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)]PF6 with "large-surface" alpha,alpha'-diimin ligands (NN)-N-boolean AND (dap = 1,12-diazaperylene, dmedap = 2,11-dimethyl-1,12-diazaperylene, dipdap = 2,11-diisopropyl-1,12-diazaperylene) and different cyclometalating ligands (CN)-N-boolean AND (piq = 1-phenylisoquinoline, bzq = benzo[h]quinoline, ppz = 1-phenylpyrazole, thpy = 2-(2-thienyl)pyridine, ppy = 2-phenylpyridine, meppy = 2-(4-methylphenyl)pyridine, dfppy = 2-(2,4-difluorophenyl)pyridine) were synthesized. The solid structures of the complexes [Ir(piq)(2)(dap)]PF6, [Ir(bzq)(2)(dap)]PF6, [Ir(ppy)(2)(dipdap)]PF6, [Ir(piq)(2)(dmedap)]PF6, [Ir(ppy)(2)(dap)]PF6 and [Ir(ppz)(2)(dap)]PF6 are reported. In [Ir(piq)(2)(dap)]PF6, the dap ligand and one of the piq ligands of each cationic complex are involved in pi-pi stacking interactions forming supramolecular channels running along the crystallographic c axis. In the crystalline [Ir(bzq)(2)(dap)]PF6 pi-pi stacking interactions between the metal complexes lead to the formation of a 2D layer structure. In addition, CH-pi interactions were found in all compounds, which are what stabilizes the solid structure. In particular, a significant number of them were found in [Ir(piq)(2)(dap)]PF6 and [Ir(bzq)(2)(dap)]PF6. The crystal structures of [Ir(ppy)(2)(dipdap)]PF6 and [Ir(ppy)(2)(dmedap)]PF6 are also presented, being the first examples of bis-cyclometalated iridium(III) complexes with phenanthroline-type alpha,alpha'-diimin ligands bearing bulky alkyl groups in the neighbourhood of the N-donor atoms. These ligands implicate a distorted octahedral coordination geometry that in turn destabilized the Ir-N-N boolean AND N bonds. The new iridium (III) complexes are not luminescent. All compounds show an electrochemically irreversible anodic peak between 1.15 and 1.58 V, which is influenced by the different cyclometalated ligands. All of the new complexes show two reversible successive one-electron "large-surface" ligand-centred reductions around -0.70 V and -1.30 V. Electrospray ionisation mass spectrometry (ESI-MS) and collision induced decomposition (CID) measurements were used to investigate the stability of the new complexes. Thereby, the stability agreed well with the order of the Ir-N-N boolean AND N bond lengths. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt30412k SN - 1477-9226 VL - 41 IS - 34 SP - 10219 EP - 10227 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Delahaye, Emilie A1 - Goebel, Ronald A1 - Loebbicke, Ruben A1 - Guillot, Regis A1 - Sieber, Christoph A1 - Taubert, Andreas T1 - Silica ionogels for proton transport JF - Journal of materials chemistry N2 - A number of ionogels - silica-ionic liquid (IL) hybrid materials - were synthesized and studied for their ionic conductivity. The materials are based on a sulfonated IL, 1-methyl-3-(3-sulfopropyl-)-imidazolium p-toluenesulfonate, [PmimSO(3)H][PTS], which contains a sulfonic acid/sulfonate group both in the IL anion and in the side chain of the IL cation. By way of the sulfonate-sulfonic acid proton transfer, the IL imparts the ionogel with a high ionic conductivity of ca. 10(-2) S cm(-1) in the as-synthesized state at 120 degrees C and 10(-3) S cm(-1) in the dry state at 120 degrees C. The ionogels are stable up to ca. 150 degrees C in dynamic thermogravimetric analysis. This suggests that these materials, which are relatively cheap and easily fabricated, could find application in fuel cells in intermediate temperature ranges where many other membrane materials are not suitable. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm00037g SN - 0959-9428 VL - 22 IS - 33 SP - 17140 EP - 17146 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Baumgartner, Jens A1 - Lesevic, Paul A1 - Kumari, Monika A1 - Halbmair, Karin A1 - Bennet, Mathieu A1 - Koernig, Andre A1 - Widdrat, Marc A1 - Andert, Janet A1 - Wollgarten, Markus A1 - Bertinetti, Luca A1 - Strauch, Peter A1 - Hirt, Ann A1 - Faivre, Damien T1 - From magnetotactic bacteria to hollow spirilla-shaped silica containing a magnetic chain JF - RSC Advances N2 - Magnetotactic bacteria produce chains of magnetite nanoparticles, which are called magnetosomes and are used for navigational purposes. We use these cells as a biological template to prepare a hollow hybrid material based on silica and magnetite, and show that the synthetic route is nondestructive as the material conserves the cell morphology as well as the alignment of the magnetic particles. The hybrid material can be resuspended in aqueous solution, and can be shown to orient itself in an external magnetic field. We anticipate that chemical modification of the silica can be used to functionalize the material surface in order to obtain multifunctional materials with specialized applications, e.g. targeted drug delivery. Y1 - 2012 U6 - https://doi.org/10.1039/c2ra20911j SN - 2046-2069 VL - 2 IS - 21 SP - 8007 EP - 8009 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Lemke, Karina A1 - Koetz, Joachim T1 - Polycation-capped CdS quantum dots synthesized in reverse microemulsions JF - Journal of nanomaterials N2 - This paper is focused on the formation and recovery of cadmium sulfide (CdS) nanoparticles in two different types of polycation-modified reverse microemulsions using low molecular weight poly(diallyldimethylammonium chloride) (PDADMAC) and poly(ethyleneimine) (PEI). Both polymers were incorporated in a quaternary w/o microemulsion consisting of water, toluene-pentanol (1 : 1), and sodium dodecyl sulfate (SDS), as well as in a ternary w/o microemulsion consisting of water, heptanol, and 3( N,N-dimethyl-dodecylammonio)-propanesulfonate (SB). UV-vis and fluorescence measurements in the microemulsion illustrate the capping effect of the polycations on the formation of the CdS quantum dots. The nanoparticles are redispersed in water and characterized by using UV-vis and fluorescence spectroscopy, in combination with dynamic light scattering. From the quaternary microemulsion, only nanoparticle aggregates of about 100 nm can be redispersed, but, from the ternary microemulsion, well-stabilized polycation-capped CdS quantum dots can be obtained. The results show that the electrostatic interactions between the polycation and the surfactant are of high relevance especially in the solvent evaporation and redispersion process. That means only that in the case of moderate polycation-surfactant interactions a redispersion of the polymer-capped CdS quantum dots without problems of aggregation is possible. Y1 - 2012 U6 - https://doi.org/10.1155/2012/478153 SN - 1687-4110 IS - 4 PB - Hindawi Publishing Corp. CY - New York ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Kirpichenko, Svetlana V. A1 - Kleinpeter, Erich T1 - Synthesis and conformational properties of 1,3-dimethyl-3-phenyl-1,3-azasilinane low temperature dynamic NMR and computational study JF - Arkivoc : free online journal of organic chemistry N2 - 1,3-Dimethyl-3-phenyl-1,3-azasilinane was synthesized and its conformational behavior was studied by the low temperature NMR spectroscopy and quantum chemical calculations. The compound was shown to exist as an equilibrium mixture of the PhaxMeeq and PheqMeax chair conformers with the N-methyl substituent in equatorial position. The barrier to ring inversion was also determined. KW - 1,3-Dimethyl-3-phenyl-1,3-azasilinane KW - conformational analysis KW - low temperature NMR spectroscopy KW - quantum chemical calculations Y1 - 2012 SN - 1551-7004 IS - 24 SP - 175 EP - 185 PB - ARKAT CY - Gainesville ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Koch, Andreas T1 - Spatial magnetic properties subject to lone pair and pi electron delocalization in benzenoid and quinoid structures are quinoid tautomers really nonaromatic? JF - Arkivoc : free online journal of organic chemistry N2 - The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of benzenoid and quinoid tautomeric structures such as benzodifurantrione and phenazine-type molecules have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept of Paul von Rague Schleyer and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the partial aromaticity of the studied compounds. In the case of the surprisingly more stable quinoid tautomers, the aromaticity-synonymous with stability due to the conjugation of p electrons and lone pairs-was not found to be particularly reduced. KW - Through-space NMR shieldings (TSNMRS) KW - GIAO KW - NICS KW - benzenoid structures KW - quinoid structures KW - aromaticity Y1 - 2012 SN - 1551-7004 SP - 94 EP - 108 PB - ARKAT CY - Gainesville ER - TY - GEN A1 - Pihlaja, Kalevi A1 - Kleinpeter, Erich T1 - Professor Ferenc Fulop a tribute T2 - Arkivoc : free online journal of organic chemistry Y1 - 2012 SN - 1551-7004 SP - 1 EP - 5 PB - ARKAT CY - Gainesville ER - TY - JOUR A1 - Najafpour, Mohammad Mahdi A1 - Hillier, Warwick A1 - Shamkhali, Amir Nasser A1 - Amini, Mojtaba A1 - Beckmann, Katrin A1 - Jaglicic, Zvonko A1 - Jagodic, Marko A1 - Strauch, Peter A1 - Moghaddam, Atefeh Nemati A1 - Beretta, Giangiacomo A1 - Bagherzadeh, Mojtaba T1 - Synthesis, characterization, DFT studies and catalytic activities of manganese(II) complex with 1,4-bis(2,2 ':6,2 ''-terpyridin-4 '-yl) benzene JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - A new di-manganese complex with "back-to-back" 1,4-bis(2,2':6,2 ''-terpyridin-4'-yl) benzene ligation has been synthesized and characterised by a variety of techniques. The back-to-back ligation presents a novel new mononuclear manganese catalytic centre that functions as a heterogeneous catalysis for the evolution of oxygen in the presence of an exogenous oxidant. We discuss the synthesis and spectroscopic characterizations of this complex and propose a mechanism for oxygen evolution activity of the compound in the presence of oxone. The di-manganese complex also shows efficient and selective catalytic oxidation of sulfides in the presence of H2O2. Density functional theory calculations were used to assess the structural optimization of the complex and a proposed reaction pathway with oxone. The calculations show that middle benzene ring is distorted respect to both of metallic centers, and this in turn leads to negligible resonance of electrons between two sides of complex. The calculations also indicate the unpaired electron located on oxyl-ligand emphasizes the radical mechanism of water oxidation for the system. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt31544k SN - 1477-9226 VL - 41 IS - 39 SP - 12282 EP - 12288 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Tiseanu, Carmen A1 - Cojocaru, Bogdan A1 - Parvulescu, Vasile I. A1 - Sanchez-Dominguez, Margarita A1 - Primus, Philipp A. A1 - Boutonnet, Magali T1 - Order and disorder effects in nano-ZrO2 investigated by micro-Raman and spectrally and temporarily resolved photoluminescence JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Pure and europium (Eu3+) doped ZrO2 synthesized by an oil-in-water microemulsion reaction method were investigated by in situ and ex situ X-ray diffraction (XRD), ex situ Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), steady state and time-resolved photoluminescence (PL) spectroscopies. Based on the Raman spectra excited at three different wavelengths i.e. 488, 514 and 633 nm and measured in the spectral range of 150-4000 cm(-1) the correlation between the phonon spectra of ZrO2 and luminescence of europium is clearly evidenced. The PL investigations span a variety of steady-state and time resolved measurements recorded either after direct excitation of the Eu3+ f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 degrees C, the overall Eu3+ emission is dominated by Eu3+ located in tetragonal symmetry lattice sites with a crystal-field splitting of the D-5(0)-F-7(1) emission of 20 cm(-1). Annealing of ZrO2 at 1000 degrees C leads to a superposition of Eu3+ emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the D-5(0)-F-7(1) transition. At all temperatures, a non-negligible amorphous/disordered content is also measured and determined to be of monoclinic nature. It was found that the evolutions with calcination temperature of the average PL lifetimes corresponding to europium emission in the tetragonal and monoclinic sites and the monoclinic phase content of the Eu3+ doped ZrO2 samples follow a similar trend. By use of specific excitation conditions, the distribution of europium on the amorphous/disordered surface or ordered/crystalline sites can be identified and related to the phase content of zirconia. The role of zirconia host as a sensitizer for the europium PL is also discussed in both tetragonal and monoclinic phases. Y1 - 2012 U6 - https://doi.org/10.1039/c2cp41946g SN - 1463-9076 VL - 14 IS - 37 SP - 12970 EP - 12981 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Suriyanarayanan, Subramanian A1 - Cywinski, Piotr J. A1 - Moro, Artur J. A1 - Mohr, Gerhard J. A1 - Kutner, Wlodzimierz ED - Haupt, K T1 - Chemosensors based on molecularly imprinted polymers JF - Topics in current chemistry JF - Topics in Current Chemistry Y1 - 2012 SN - 978-3-642-28421-2 U6 - https://doi.org/10.1007/128_2010_92 SN - 0340-1022 VL - 325 IS - 4 SP - 165 EP - 265 PB - Springer CY - Berlin ER - TY - JOUR A1 - Nagy, Zsuzsanna T. A1 - Heinrich, Benoit A1 - Guillon, Daniel A1 - Tomczyk, Jaroslaw A1 - Stumpe, Joachim A1 - Donnio, Bertrand T1 - Heterolithic azobenzene-containing supermolecular tripedal liquid crystals self-organizing into highly segregated bilayered smectic phases JF - Journal of materials chemistry N2 - Synthesis, self-organization, and optical properties of supermolecular tripedal liquid crystals incorporating various prototypical mesogenic units such as alkoxy-azobenzene (AZB), alkoxy-biphenylene (BPH) or alkoxy-cyanobiphenyl (OCB) derivatives are reported. Different molecular systems were designed in order to sequentially incorporate the smectogenic-like alkoxy-azobenzene-based chromophore within the molecular structure, whose relative proportion is selectively varied by exchanging with the other mesogens. A divergent synthetic mode was elaborated for their synthesis, starting from the regioselective functionalization of the phloroglucinol-based (PG) inner core. This methodology allowed the preparation of several sets of unconventional tripedal oligomers with conjugated heterolithic structures (made of different blocks, e.g. PG(6)AZB(x)BPH(3-x) and PG(6)AZB(x)OCB(3-x), x = 1 or 2) along the homolithic parents (all identical blocks, e.g. PG(z)AZB(3), z = 6 or 11, z is the number of methylene in the spacer between PG and the protomesogen, PG(6)BPH(3), and PG(6)OCB(3)), respectively. Essentially all the synthesized systems behave as thermotropic liquid crystals and show various types of highly segregated multilayered smectic phases, or, in one case, a nematic phase, depending on the nature of the constitutive anisotropic blocks and on the molecular topology (homolithic versus heterolithic, mesogenic ratio x : 3 - x). The effects of these structural modifications on the mesomorphism (mesophase structures, temperature ranges, and thermodynamic stability) have been investigated by differential scanning calorimetry and small-angle X-ray diffraction experiments combined with dilatometric measurements. Models describing the various supramolecular organizations of these tripedes into such multilayered structures are proposed and discussed. Preliminary results of the investigations of their optical properties will also be presented. Y1 - 2012 U6 - https://doi.org/10.1039/c2jm33751g SN - 0959-9428 VL - 22 IS - 35 SP - 18614 EP - 18622 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Ghobadi, Ehsan A1 - Heuchel, Matthias A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Simulation of volumetric swelling of degradable poly[(rac-lactide)-co-glycolide] based polyesterurethanes containing different urethane-linkers JF - Journal of applied biomaterials & functional materials N2 - Aim: The hydrolytic degradation behavior of degradable aliphatic polyester-based polymers is strongly influenced by the uptake or transport of water into the polymer matrix and also the hydrolysis rate of ester bonds. Methods: We examined the volumetric swelling behavior of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based polyurethanes (PLGA-PU) with water contents of 0 wt%, 2 wt% and 7 wt% water at 310 K using a molecular modeling approach. Polymer systems with a number average molecular weight of M-n = 10,126 g.mol(-1) were constructed from PLGA with a lactide content of 67 mol%, whereby PLGA-PU systems were composed of five PLGA segments with M-n = 2052 g.mol(-1), which were connected via urethane linkers originated from 2,2,4-trimethyl hexamethylene-1,6-diisocyanate (TMDI), hexamethyl-1,6-diisocyanate (HDI), or L-lysine-1,6-diisocyanate (LDI). Results: The calculated densities of the dry PLGA-PU systems were found to be lower than for pure PLGA. The obtained volumetric swelling of the PLGA-PU was depending on the type of urethane linker, whereby all swollen PLGA-PUs contained larger free volume distribution compared to pure PLGA. The mean square displacement curves for dry PLGA and PLGA-PUs showed that urethane linker units reduce the mobility of the polymer chains, while an increase in backbone atoms mobility was found, when water was added to these systems. Consequently, an increased water uptake of PLGA-PU matrices combined with a higher mobility of the chain segments should result in an accelerated hydrolytic chain scission rate in comparison to PLGA. Conclusions: It can be anticipated that the incorporation of urethane linkers might be a helpful tool to adjust the degradation behavior of polyesters. KW - Hydrolytic degradation KW - Molecular dynamics simulation KW - Polyesterurethane Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10432 SN - 2280-8000 VL - 10 IS - 3 SP - 293 EP - 301 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Friess, Fabian A1 - Wischke, Christian A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Oligo(epsilon-caprolactone)-based polymer networks prepared by photocrosslinking in solution JF - Journal of applied biomaterials & functional materials N2 - Purpose: Polymer networks with adjustable properties prepared from endgroup-functionalized oligoesters by UV-crosslinking in melt have evolved into versatile multifunctional biomaterials. In addition to the molecular weight or architecture of precursors, the reaction conditions for crosslinking are pivotal for the polymer network properties. Crosslinking of precursors in solution may facilitate low-temperature processes and are compared here to networks synthesized in melt. Methods: Oligo(epsilon-caprolactone)-(z) methacrylate (oCL-(z) IEMA) precursors with a linear (z = di) or a four-armed star-shaped (z = tetra) architecture were crosslinked by radical polymerization in melt or in solution with UV irradiation. The thermal, mechanical, and swelling properties of the polymer networks obtained were characterized. Results: Crosslinking in solution resulted in materials with lower Young's moduli (E), lower maximum stress (sigma(max)), and higher elongation at break (epsilon(B)) as determined at 70 degrees C. Polymer networks from 8 kDa star-shaped precursors exhibited poor elasticity when synthesized in the melt, but can be established as stretchable materials with a semi-crystalline morphology, a high gel-content, and a high elongation at break when prepared in solution. Conclusions: The crosslinking condition of methacrylate functionalized precursors significantly affected network properties. For some types of precursors such as star-shaped telechelics, synthesis in solution provided semi-crystalline elastic materials that were not accessible from crosslinking in melt. KW - Crosslinking KW - Methacrylate KW - Multifunctional polyester networks KW - Poly(epsilon-caprolactone) KW - Polymer network properties Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10372 SN - 2280-8000 VL - 10 IS - 3 SP - 273 EP - 279 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Ghobadi, Ehsan A1 - Heuchel, Matthias A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Influence of different heating regimes on the shape-recovery behavior of poly(L-lactide) in simulated thermomechanical tests JF - Journal of applied biomaterials & functional materials N2 - Aim: Multifunctional polymer-based biomaterials, which combine degradability with a shape-memory capability and in this way enable the design of actively moving implants such as self-anchoring implants or controlled release systems, have been recently introduced. Of particular interest are approved degradable polymers such as poly(L-lactide) (PLLA), which can be easily functionalized with a shape-memory effect. In the case of semicrystalline PLLA, the glass transition can be utilized as shape-memory switching domain. Methods: In this work we applied a fully atomistic molecular dynamics simulation to study the shape-memory behavior of PLLA. A heating-deformation-cooling programming procedure was applied to atomistic PLLA packing models followed by a recovery module under stress-free conditions allowing the shape recovery. The recovery was simulated by heating the samples from T-low = 250 K to T-high = 500 K with different heating rates beta of 125, 40 and 4 K.ns(-1). Results: We could demonstrate that the obtained strain recovery rate (R-r) was strongly influenced by the applied simulation time and heating rate, whereby R-r values in the range from 46% to 63% were achieved. On its own the application of a heating rate of 4 K.ns(-1) enabled us to determine a characteristic switching temperature of T-sw = 473 K for the modeled samples. Conclusions: We anticipate that the atomistic modeling approach presented should be capable of enabling further study of T-sw with respect to the molecular structure of the investigated SMP and therefore could be applied in the context of design and development of new shape-memory (bio) materials. KW - Molecular modeling KW - Polymers KW - Shape-memory effect Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10440 SN - 2280-8000 VL - 10 IS - 3 SP - 259 EP - 264 PB - Wichtig CY - Milano ER - TY - JOUR A1 - von Rüsten-Lange, Maik A1 - Luetzow, Karola A1 - Neffe, Axel T. A1 - Lendlein, Andreas T1 - Characterization of oligo(ethylene glycol) and oligoglycerol functionalized poly(ether imide) by angle-dependent X-ray photoelectron spectroscopy JF - Journal of applied biomaterials & functional materials N2 - Purpose: Previous investigations have shown that poly(ether imide) (PEI) membranes can be functionalized with aminated macromolecules. In this study we explored whether the characterization of PEI functionalized with oligo(ethylene glycol) (OEG) or linear, side chain methylated oligoglycerols (OGMe), by angle-dependent X-ray induced photoelectron spectroscopy (XPS) can be used to prove the functionalization, give insight into the reaction mechanism and reveal the spatial distribution of the grafts. Methods: PEI membranes were functionalized under alkaline conditions using an aqueous solution with 2 wt% of alpha-amino-methoxy oligo(ethylene glycol) (M-n = 1,320 g.mol(-1)) or linear, side chain methylated monoamine oligoglycerols (M-n = 1,120, 1,800 or 2,270 g.mol(-1)), respectively. The functionalized membranes were investigated using XPS measurements at different detector angles to enable comparison between the signals related to the bulk and surface volume and were compared with untreated and alkaline-treated PEI membranes. Results: While at a perpendicular detector angle the bulk signals of the PEI were prominent, at larger surface volume-related detector angles, the signals for OGMe and OEG were determinable. Conclusion: The surface functionalization of PEI with OEG and OGMe could be verified by the angle-dependent XPS. The observations proved the functionalization at the PEI surface, as the polyethers were detected at angles providing signals of the surface volume. Furthermore, the chemical functions determined verified a covalent binding via the nucleophilic addition of the amine functionalized OGMe and OEG to the PEI imide function. KW - Poly(ether imide) KW - Oligo(ethylene glycol) KW - Oligoglycerols KW - Angle-dependent X-ray induced photoelectron spectroscopy KW - Surface functionalization Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10345 SN - 2280-8000 VL - 10 IS - 3 SP - 215 EP - 222 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Wang, Li A1 - Heuchel, Matthias A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Influence of a polyester coating of magnetic nanoparticles on magnetic heating behavior of shape-memory polymer-based composites JF - Journal of applied biomaterials & functional materials N2 - Background: Magnetic composites of thermosensitive shape-memory polymers (SMPs) and magnetite nanoparticles (MNPs) allow noncontact actuation of the shape-memory effect in an alternating magnetic field. In this study, we investigated whether the magnetic heating capability of cross-linked poly(epsilon-caprolactone)/MNP composites (cPCLC) could be improved by covalent coating of MNPs with oligo(epsilon-caprolactone) (OCL). Methods: Two different types of cPCLC containing uncoated and OCL-coated MNP with identical magnetite weight content were prepared by thermally induced polymerization of poly(epsilon-caprolactone) diisocyanatoethyl methacrylate. Both cPCLCs exhibited a melting transition at T-m = 48 degrees C, which could be used as switching transition. Results: The dispersion of the embedded nanoparticles within the polymer matrix could be substantially improved, when the OCL-coated MNPs were used, as visualized by scanning electron microscopy. We could further demonstrate that in this way the maximal achievable bulk temperature (T-bulk) obtained within the cPCLC test specimen in magnetic heating experiments at a magnetic field strength of H = 30 kA.m(-1) could be increased from T bulk = 48 degrees C to T bulk = 74 degrees C. KW - Magnetic composites KW - Magnetite nanoparticles KW - Polymer networks KW - Shape-memory effect Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10293 SN - 2280-8000 VL - 10 IS - 3 SP - 203 EP - 209 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Melchert, Christian A1 - Yongvongsoontorn, Nunnarpas A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Synthesis and characterization of telechelic oligoethers with terminal cinnamylidene acetic acid moieties JF - Journal of applied biomaterials & functional materials N2 - Purpose: The formation of photoresponsive hydrogels were reported by irradiation of star-shaped poly(ethylene glycol)s with terminal cinnamylidene acetic acid (CAA) groups, which are capable of a photoinduced [2+2] cycloaddition. In this study we explored whether oligo(ethylene glycol) s and oligo(propylene glycol)s of varying molecular architecture (linear or star-shaped) or molecular weights could be functionalized with CAA as terminal groups by esterification or by amide formation. Methods: Oligo(ethylene glycol) (OEG) and oligo(propylene glycol) (OPG) with varying molecular architecture (linear, star-shaped) and weight average molecular weights between 1000 and 5000 g.mol(-1) were functionalized by means of esterification of hydroxyl or amine endgroups with cinnamylidene acetic acid (CAA) or cinnamylidene acetyl chloride (CAC) as telechelic endgroups. The chemical structure, thermal properties, and molecular weights of the oligoethers obtained were determined by NMR spectroscopy, UV spectroscopy, DSC, and MALDI-TOF. Results: CAA-functionalized linear and star-shaped OEGs or OPGs could be obtained with a degree of functionalization higher than 90%. In MALDI-TOF measurements an increase in Mw of about 150 g.mol(-1) (for each terminal end) after the functionalization reaction was observed. OEGCAA and OPGCAA showed an increase in glass transition temperature (T-g) from about -70 degrees C to -50 degrees C, compared to the unfunctionalized oligoethers. In addition, the melting temperature (T-m) of OEGCAA decreased from about 55 C to 30 degrees C, which can be accounted for by the hampered crystallization of the precursors because of the bulky CAA end groups as well as by the loss of the hydroxyl telechelic end groups. Conclusion: The synthesis of photoresponsive oligoethers containing cinnamylidene acetic acid as telechelic endgroup was reported and high degrees of functionalization could be achieved. Such photosensitive oligomers are promising candidates as reactive precursors, for the preparation of biocompatible high molecular weight polymers and polymer networks. KW - Biocompatible polymers KW - Cinnamylidene acetic acid KW - Photoresponsive polymers Y1 - 2012 U6 - https://doi.org/10.5301/JABFM.2012.10364 SN - 2280-8000 VL - 10 IS - 3 SP - 185 EP - 190 PB - Wichtig CY - Milano ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Kleinpeter, Erich T1 - Conformational preferences of Si-Ph,H and Si-Ph,Me silacyclohexanes and 1,3-thiasilacyclohexanes. Additivity of conformational energies in 1,1-disubstituted heterocyclohexanes JF - Tetrahedron N2 - The conformational equilibria of 1-phenyl-1-silacyclohexane 1, 3-phenyl-1,3-thiasilacyclohexane 2, 1-methyl-1-phenyl-1-silacyclohexane 3, and 3-methyl-3-phenyl-1,3-thiasilacyclohexane 4 have been studied for the first time by low temperature C-13 NMR spectroscopy at 103 K. Predominance of the equatorial conformer of compound 1 (Ph-eq/Ph-ax=78%:22%) is much less than in its carbon analog, phenylcyclohexane (nearly 100% of Ph-eq). And in contrast to 1-methyl-1-phenylcyclohexane, the conformers with the equatorial Ph group are predominant for compounds 3 and 4: at 103 K, Ph-eq/Ph-ax ratios are 63%:37% (3) and 68%:32% (4). As the Si-C bonds are elongated with respect to C-C bonds, the barriers to ring inversion are only between 5.2-6.0 (ax -> eq) and 5.4-6.0 (eq -> ax) kcal mol(-1). Parallel calculations at the DFT and MP2 level of theory (as well as the G2 calculations for compound 1) show qualitative agreement with the experiment. The additivity/nonadditivity of conformational energies of substituents on cyclohexane and silacyclohexane derivatives is analyzed. The geminally disubstituted cyclohexanes containing a phenyl group show large deviations from additivity, whereas in 1-methyl-1-phenyl-1-silacyclohexane and 3-methyl-3-phenyl-1,3-thiasilacyclohexane the effects of the methyl and phenyl groups are almost additive. The reasons for the different conformational preferences in carbocyclic and heterocyclic compounds are analyzed using the homodesmotic reactions approach. KW - Conformational analysis KW - Heterocycles KW - Dynamic NMR KW - Theoretical calculations KW - Additivity of conformational energies Y1 - 2012 U6 - https://doi.org/10.1016/j.tet.2011.10.082 SN - 0040-4020 VL - 68 IS - 1 SP - 114 EP - 125 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Kirpichenko, Svetlana V. A1 - Shlykov, Sergei A. A1 - Keinpeter, Erich T1 - Structure and conformational properties of 1,3,3-Trimethyl-1,3-Azasilinane gas electron diffraction, dynamic NMR, and theoretical study JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - Structure and the conformational properties of 1,3,3-trimethyl-1,3-azasilinane have been studied. According to gas electron diffraction (GED), the molecule exists in a slightly distorted chair conformation with the N-Me group in equatorial position. High-level quantum chemical calculations excellently, reproduce the experimental geometry. Employing variable temperature H-1 and C-13 NMR spectroscopy down to 103 K, the conformational equilibrium could be frozen and the barrier to ring inversion determined. Y1 - 2012 U6 - https://doi.org/10.1021/jp2110852 SN - 1089-5639 VL - 116 IS - 1 SP - 784 EP - 789 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Barth, Johannes A1 - Siegmann, Rebekka A1 - Beuermann, Sabine A1 - Russell, Gregory T. A1 - Buback, Michael T1 - Investigations into chain-length-dependent termination in bulk radical polymerization of 1H, 1H, 2H, 2H-Tridecafluorooctyl methacrylate JF - Macromolecular chemistry and physics N2 - The SP-PLP-EPR technique is used to carry out a detailed investigation of the radical termination kinetics of 1H, 1H, 2H, 2H-tridecafluorooctyl methacrylate (TDFOMA) in bulk at relatively low conversion. Composite-model behavior for chain-length-dependent termination rate coefficients, kti,i, is observed. It is found that for TDFOMA, ic approximate to 60 independent of temperature, and as approximate to 0.65 and al approximate to 0.2 at 80 degrees C and above. However, at lower temperatures the situation is strikingly different, with the significantly higher average values of as = 0.89 +/- 0.15 and al = 0.32 +/- 0.10 being obtained at 50 degrees C and below. This makes TDFOMA the first monomer to be found that exhibits clearly different exponent values, as and al, at lower and higher temperature, and that has both a high as, like an acrylate, and a high ic, like a methacrylate. KW - ESR KW - EPR KW - kinetics (polym KW - ) KW - methacrylates KW - radical polymerization KW - termination Y1 - 2012 U6 - https://doi.org/10.1002/macp.201100479 SN - 1022-1352 VL - 213 IS - 1 SP - 19 EP - 28 PB - Wiley-Blackwell CY - Malden ER - TY - JOUR A1 - Lazareva, Nataliya F. A1 - Albanov, Alexander I. A1 - Shainyan, Bagrat A. A1 - Kleinpeter, Erich T1 - Synthesis and conformational properties of substituted 1,4,2-oxazasilinanes low temperature NMR study and quantum chemical calculations JF - Tetrahedron N2 - A number of N-substituted 2,2-dimethyl-1,4,2-oxazasilinanes 1 were synthesized and studied by variable temperature dynamic H-1 and C-13 NMR spectroscopy, room temperature N-15 NMR spectroscopy and theoretical calculations at the DFT and MP2 levels of theory. Both the preferred conformers were assigned and the barrier to the ring inversion of the saturated six-membered ring determined. From 1 the corresponding methyl iodide salts were produced, their structure studied by X-ray analysis and found to be in excellent agreement with the results of the theoretical calculations. KW - 1,4,2-Oxazasilinanes KW - Conformational analysis KW - Dynamic NMR KW - X-ray analysis KW - Quantum chemical calculations Y1 - 2012 U6 - https://doi.org/10.1016/j.tet.2011.11.077 SN - 0040-4020 VL - 68 IS - 4 SP - 1097 EP - 1104 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schmidt, Bernd A1 - Kunz, Oliver T1 - One-Flask tethered ring closing Metathesis-Electrocyclic ring opening for the highly stereoselective synthesis of conjugated Z/E-Dienes JF - European journal of organic chemistry N2 - A one-flask reaction sequence comprising ring closing metathesis (RCM) of butenoates derived from allylic alcohols and a base-mediated ring opening gives 2Z,4E-configured dienoic acids in high yields and stereoselectivities. Application of the method to the synthesis of the natural product fusanolide A suggests that the originally published structure was erroneously assigned and should be revised. KW - Natural products KW - Lactones KW - Macrocycles KW - Metathesis KW - Carboxylic -acids Y1 - 2012 U6 - https://doi.org/10.1002/ejoc.201101497 SN - 1434-193X IS - 5 SP - 1008 EP - 1018 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Neuvonen, Kari A1 - Neuvonen, Helmi A1 - Koch, Andreas A1 - Kleinpeter, Erich T1 - Taft equation in the light of NBO computations introduction of a novel polar computational substituent constant scale sigma(q)* for alkyl groups JF - Computational and theoretical chemistry N2 - The validity of the Taft equation: log(k(R)/k(CH3)) = rho*sigma* + delta E-S was studied with the aid of NBO computational results concerning cyclohexyl esters RCOOC6H11 [R = Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec-Butyl, tert-Butyl, Neopentyl, CH(CH2CH3)(2), CH(CH3)C(CH3)(3), C(CH3)(2)CH2CH3, C(CH3)(2)C(CH3)(3), CH(CH3)(Np), CH(iPr)(tBu), C(Me)(Et)(iPr), C(Et)(2)(tBu) or C(Et)(iPr)(tBu)]. It was proved that the sigma*(alkyl) value is a composite substitutent constant including the polar and steric contributions. A novel computational sigma(q)* substituent constant scale is presented based on the NBO atomic charges of the alpha-carbon and the computational total steric exchange energies E(ster) of the cyclohexyl esters specified above. The method used offers a useful way to calculate sigma*(alkyl) values for alkyl groups for which experimental Taft's polar sigma* parameters are not available. KW - NBO analysis KW - Taft equation KW - Polar substituent constant KW - Steric effect Y1 - 2012 U6 - https://doi.org/10.1016/j.comptc.2011.11.044 SN - 2210-271X VL - 981 IS - 2 SP - 52 EP - 58 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Winter, Alette A1 - Zabel, Andre A1 - Strauch, Peter T1 - Tetrachloridocuprates(II)-Synthesis and Electron Paramagnetic Resonance (EPR) Spectroscopy JF - International journal of molecular sciences N2 - Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl4](2-), with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g parallel to and g perpendicular to) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids. KW - tetrachloridocuprate(II) KW - electron paramagnetic resonance KW - copper(II) KW - ionic liquid Y1 - 2012 U6 - https://doi.org/10.3390/ijms13021612 SN - 1661-6596 VL - 13 IS - 2 SP - 1612 EP - 1619 PB - MDPI CY - Basel ER -