Carboxylic Acid Ligands Research Articles

Template-Assisted Synthesis of Co,Mn-MOFs with Magnetic Properties Based on Pyridinedicarboxylic Acid

To investigate the influence of organic molecules with reactive functional groups as templates on the structures of the resulting MOFs, four novel complexes based on the pyridyl carboxylic acid ligand 5-(pyridin-4-yl)isophthalic acid (H2pyip), namely, [Mn3(pyip)2(HCOO)2(H2O)2]n (1), {[Co(pyip)(H2O)]·H2O}n (2), {[Mn2(pyip)2(H2O)4]·5H2O}n (3), and [Co(pyip)(EtOH)(H2O)]n (4), have been synthesized under solvothermal conditions. In the presence of 4,4′-bipyridyl as the template, 3D coordination framework 1 with the Schlafli symbol of (4·6·7) (42·5·65·73·82·9·11) was obtained. Using cyanoacetic acid as the template, we obtained 2D double-layered structure 2 with the Schlafli symbol of (43) (46·66·83). 3 and 4 are prepared in the absence of a templating agent. 3 features an infinite 2D network with a 1D water chain penetrating the 1D channel and further results in a 3D supramolecule through hydrogen-bond interactions. 4 contains two independent 2D networks that are further connected to a 2D double-layered supra...

A synthetic quest for tris(imidazolyl) carboxylates and their metal complexes: active site models for quercetin 2,3-dioxygenases and other non-heme redox metalloenzymes

Synthetic routes to tris(imidazolyl)carboxylate ligands and representative metal complexes are reported, which provide more accurate active site models for several classes of redox metalloenzymes. In the first route a hydroxypivalate ester is converted in four regioselective steps to an imidazole diester 4; this is then converted to tris(imidazolyl)carboxylic acid ligand 9, featuring regiospecific double addition of an N-protected lithio-imidazole to an imidazole diester 8. Ligand 9 forms a Co(III) complex, (9)(9-H)Co (10), characterized by X-ray diffraction, coordinated via two imidazole units and the carboxylate. A second route was developed, which provides more soluble ligands that are less prone to form oligomeric complexes. It utilizes addition of the Grignard reagent from 4-iodo-2-isopropylimidazole 12 to an imidazole diester 13, producing atropisomeric tris(imidazolyl)carbinol esters 15M. Treatment of 15M with [Cu(CH3CN)4]PF6 gives a trinuclear complex 16 having alkoxide bridges between neighboring Cu atoms. A third route avoids the bridging alkoxo groups by reduction of tris(imidazolyl)carbinol 15M to the tris(imidazolyl)methane ester 17, which is hydrolyzed to the tris(imidazolyl)methane carboxylic acid 11a. This ligand reacts with [Cu(CH3CN)4]PF6 to produce dinuclear complex [(11a-H)2Cu2](PF6)2 (18), whose X-ray crystal structure shows each copper in a distorted square pyramidal geometry with coordination to the three imidazoles and two bridging carboxylate oxygens. Complex 18 is geometrically similar to the active site copper in quercetin 2,3-dioxygenase.

Zn(ii) and Cd(ii) coordination polymers assembled by di(1H-imidazol-1-yl)methane and carboxylic acid ligands

Five new Zn(II)/Cd(II) coordination polymers constructed from di(1H-imidazol-1-yl)methane (L) mixed with different auxiliary carboxylic acid ligands formulated as [Zn(L)(H(2)L(1))(2)·(H(2)O)(0.2)](n) (1), {[Zn(L)(L(2))]·H(2)O}(n) (2), {[Cd(2)(L)(2)(L(2))(2)]·2H(2)O}(n) (3), {[Cd(L)(L(3))]·H(2)O}(n) (4) and [Cd(L)(L(4))](n) (5) (H(3)L(1) = 1,3,5-benzenetricarboxylic acid, H(2)L(2) = 4,4'-oxybis(benzoic acid), H(2)L(3) = m-phthalic acid and H(2)L(4) = p-phthalic acid) have been synthesized under hydrothermal conditions and structurally characterized. Four related auxiliary carboxylic acids were chosen to examine the influences on the construction of these coordination frameworks with distinct dimensionality and connectivity. The coordination arrays of 1-5 vary from 1D zigzag chain for 1, 2D (4,4) layer for 2-4, to 2-fold interpenetrated 3D coordination network with the α-Po topology for 5. The thermal and photoluminescence properties of complexes 1-5 in the solid state have also been investigated.

One-pot synthesis of two pillar-layer frameworks: coordination polymorphs deriving from different linking modes of 1,3,5-benzenetricarboxylate

In this work, the aromatic polycarboxylic acid, 1,3,5-benzenetricarboxylate (H3btc), has been utilized as a variable building block to perform an intensive study on the structure diversity of coordination polymorphs. The one-pot solvothermal reaction of Ni(NO3)2 with H3btc and 1,4-bis(imidazolyl)benzene (bib) ligands affords two novel polymorphous coordination polymers, {[Ni2(Hbtc)2(bib)3]·(H2O)}∞ (1) and {[Ni3(btc)2(bib)3(H2O)2]·(CH3OH)(H2O)4}∞ (2). In polymorphs 1 and 2, the aromatic acid adopts different bridging modes (κ1)-(κ1)-(κ1)-μ3 and (κ1)-(κ2)-(κ1-κ1)-μ4 to connect nickel ions into 2D (6,3) and (4,4) layers, which are further pillared by the bib ligand to form two binodal pillar-layer frameworks with Schäfli symbols of [63]·[614.8] and [44.62]·[48.67], respectively. The two polymorphs both exhibit a nickel–bib matrix, but the carboxylic acid ligand takes various coordination modes, finally leading to diverse topological structures. Furthermore, the deprotonation style of 1,3,5-benzenetricarboxylate steers the number of coordination mode around the metal ion, specifically the partially deprotonated Hbtc2− relating to one geometry-independent metal ion, and the fully deprotonated btc3− associating with two crystallographically independent metal ions. The variety of topological structure and metal composition indicates that the ligand H3btc plays an essential role in the assembly of the coordination polymorph. Magnetic studies reveal the weak ferromagnetic interaction within the binuclear cluster of polymorph 2.

Mixed-ligand manganese(II)-phenolate complexes: study of DNA cleavage, cytotoxic activity, and induction of apoptosis

Two manganese complexes, [Mn(L1)2(dibe)2](L1) (1) and [Mn(L2)2(dibe)2] (2) (where L1 = 2,2′-bipyridine (bipy), L2 = 1,10-phenanthroline (phen)), were synthesized by using a carboxylic acid ligand (dibe = 2,2-dibenzylmalonate acid). The two complexes were characterized using IR, elemental analysis, and X-ray crystallography. Fluorescence analysis indicates that the two complexes can bind to HeLa cell DNA (HC-DNA), and gel electrophoresis assay demonstrates the ability of the complexes to cleave the HC-DNA. The two complexes exhibit cytotoxic specificity and significant cancer cell inhibitory rate. Furthermore, apoptotic tests demonstrate that these two complexes have apoptotic effects on HeLa cells.

Molecular and spectroscopic properties of hydridecarbonyl ruthenium complexes with pyrazine carboxylic acid ligands

The hydride carbonyl ruthenium(II) [RuH(CO)(pyzCOO)(PPh 3) 2] ( 1), [RuH(CO)(pyz-2,3-COO[CH 3])(PPh 3) 2]·H 2O ( 2) and dinuclear Ru(II)/Ru(III) [RuH(CO)(PPh 3)(pyz-2,3-COO)Ru(CO)Cl 2(PPh 3) 2] ( 3) complexes were synthesized and characterized by IR, 1H, 31P NMR, UV–Vis spectroscopy and X-ray crystallography. The experimental studies were complemented by quantum chemical calculations, which were used to identify the nature of the interactions between the ligands and the central ion, and the orbital composition in the frontier electronic structure. Based on a molecular orbital scheme, the calculated results allowed the interpretation of the UV–Vis spectra obtained at an experimental level. The luminescence property of the complex 2 was determined. The ac magnetic susceptibility measurements showed a residual magnetism evidenced by the small values of the molar susceptibility, not exceeding 0.5 emu/mol at 2 K, a lack of a Curie-Weiss region and weak magnetic interactions below 20 K.

Synthesis, characterization and crystal structures of 2-[(E)-2-(4-hydroxy-3,5-dimethylphenyl)-1-diazenyl]benzoic acid and its polymeric and monomeric triorganotin(IV) complexes

Three triorganotin(IV) complexes of composition R 3SnLH (R = Me, Bu and Ph and LH = 2-[(E)-2-(4-hydroxy-3,5-dimethylphenyl)-1-diazenyl]benzoate) have been synthesized and characterized by 1H, 13C, 119Sn NMR, and IR spectroscopic techniques in combination with elemental analysis. The crystal structures of the carboxylate ligand HO 2CC 6H 4{N N(C 6H 2-4-OH-3,5-(CH 3) 2)}- o in its neutral form and three triorganotin(IV) complexes, viz., polymeric (R 3Sn[O 2CC 6H 4{N–N(H)(C 6H 2-4-O-3,5-(CH 3) 2)}- o]) n (R = Me ( 1) and Bu ( 2)) and monomeric Ph 3Sn[O 2CC 6H 4{N–N(H)(C 6H 2-4-O-3,5-(CH 3) 2)}- o] ( 3) complexes are reported. The polymeric complexes 1 and 2 exist as extended chains in which the LH-bridged Sn-atoms adopt a trans-R 3SnO 2 trigonal bipyramidal configuration with R groups in the equatorial positions and the axial sites occupied by an oxygen atom from the carboxylate ligand and the phenoxide O atom of the next carboxylate ligand. The Sn atom in complex 3 has a distorted tetrahedral geometry. In all three complexes, the carboxylate ligand is in the zwitterionic form with the phenolic proton moved to the nearby azo nitrogen atom, in contrast to the free carboxylic acid ligand which is in the azo form.

C-H arylation of pyridines: high regioselectivity as a consequence of the electronic character of C-H bonds and heteroarene ring.

We report a new catalytic protocol for highly selective C-H arylation of pyridines containing common and synthetically versatile electron-withdrawing substituents (NO(2), CN, F and Cl). The new protocol expands the scope of catalytic azine functionalization as the excellent regioselectivity at the 3- and 4-positions well complements the existing methods for C-H arylation and Ir-catalyzed borylation, as well as classical functionalization of pyridines. Another important feature of the new method is its flexibility to adapt to challenging substrates by a simple modification of the carboxylic acid ligand or the use of silver salts. The regioselectivity can be rationalized on the basis of the key electronic effects (repulsion between the nitrogen lone pair and polarized C-Pd bond at C2-/C6-positions and acidity of the C-H bond) in combination with steric effects (sensitivity to bulky substituents).

Spectroscopic studies on some fluorescent mixed-ligand titanium(IV) complexes

A novel route to synthesize some titanium(IV) complexes containing acetylacetone, straight chain carboxylic acid and hydroxycarboxylic acid ligands has been investigated. Complexes with the general formula [Ti(acac)Cl 2− n (OOCR*) n (OOCC 15H 31)] (where Hacac = acetylacetone, R*COOH = hydroxycarboxylic acids and n = 1 or 2) have been isolated and characterized. Molecular weight determinations indicated mononuclear nature of the complexes. LMCT bands were observed in the electronic spectra. Infrared spectra suggested bidentate nature of the ligands. Fluorescent behaviour of the complexes was noticed on the basis of fluorescence spectra. Powder XRD indicated them to be semi-crystalline having the crystallite size in 136–185 nm range. Transmission electron microscopy (TEM) indicated spherical particles of ∼200 nm diameter. On the basis of physico-chemical studies, it is suggested that titanium is having coordination number 7 or 8 in these complexes.

A copper(II) complex with neutral carboxylic acid ligand

A copper(II) complex with neutral carboxylic acid ligand

Mobile Surface Traps in CdSe Nanocrystals with Carboxylic Acid Ligands

We have performed ab initio calculations of electronic properties of the realistic Cd-rich CdSe nanocrystals with covalently bound carboxylic acid (X-type) ligands. Configurations both with and without surface traps can be prepared depending on the amount and geometry of the adsorbed ligands. We find that Cd and Se dangling bonds do not necessarily create surface traps, whereas traps originating from ligands can form near the top of the valence band. Some of the ligands are found to be mobile on the surface and this mobility is accompanied by a spectral diffusion of the associated trap energy levels. This provides the first atomistic example of the processes required to explain the emission wavelength and lifetime variations, and blinking of the nanocrystals.

Synthesis, structure and properties of one novel 2D Mn-heterocyclic carboxylic acid complex [Mn(TPA)Cl(H 2O)] n

A novel 2D layer complex [Mn(TPA)Cl(H 2O)] n ( 1) has been synthesized by two methods through the reaction of MnCl 2 and TPC or TPA under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis, infrared spectrometry (IR), powder X-ray diffraction (XRD) and thermogravimetric analysis (TGA), where heterocyclic carboxylic acid ligand TPA = 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetic acid, TPC = 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetonitrile. The distorted octahedral Mn(II) centers are bridged by carboxylic O atoms resulting in the formation of a 1D chain. Then the 1D chains are connected with each other through TPA ligands into a 2D (3,3)-connected topology framework. The H-bonding interactions extend the complex into a three-dimensional network, and such weak interactions further stabilized the complex. Furthermore, solid-state fluorescence spectrum of complex 1 exhibits intense broad emissions at 396 nm at room temperature, which is red-shifted by 21 nm relative to that of free ligand TPA.

Utilizing Self-Exchange To Address the Binding of Carboxylic Acid Ligands to CdSe Quantum Dots

We use solution NMR techniques to analyze the organic/inorganic interface of CdSe quantum dots (Q-CdSe) synthesized using oleic acid as a surfactant. It is shown that the resulting Q-CdSe are stabilized by tightly bound oleic acid species that only exchange upon addition of free oleic acid. The NMR analysis points toward a two-step exchange mechanism where free ligands are initially physisorbed within the ligand shell to end up as bound, chemisorbed ligands in a second step. Importantly, we find that every ligand is involved in this exchange process. By addition of oleic acid with a deuterated carboxyl headgroup, we demonstrate that the bound ligands are oleate ions and not oleic acid molecules. This explains why a dynamic adsorption/desorption equilibrium only occurs in the presence of excess free oleic acid, which donates the required proton. Comparing the number of oleate ligands to the excess cadmium per CdSe quantum dot, we find a ratio of 2:1. This completes the picture of Q-CdSe as organic/inorganic entities where the surface excess of Cd(2+) is balanced by a double amount of oleate ligands, yielding overall neutral nanoparticles.

Distance-dependent Fluorescence Quenching and Binding of CdSe Quantum Dots by Functionalized Nitroxide Radicals.

Quantum dot (QD) fluorescence is effectively quenched at low concentration by nitroxides bearing amine or carboxylic acid ligands. The association constants and fluorescence quenching of CdSe QDs with these derivatized nitroxides have been examined using electron paramagnetic resonance (EPR) and fluorescence spectroscopy. The EPR spectra in the non-protic solvent toluene are extremely sensitive to intermolecular and intramolecular hydrogen bonding of the functionalized nitroxides. Fluorescence measurements show that quenching of QD luminescence is nonlinear, with a strong dependence on the distance between the radical and the QD. The quenched fluorescence is restored when the surface-bound nitroxides are converted to hydroxylamines by mild reducing agents, or trapped by carbon radicals to form alkoxyamines. EPR studies indicate that photoreduction of the nitroxide occurs in toluene solution upon photoexcitation at 365 nm. However, photolysis in benzene solution gives no photoreduction, suggesting that photoreduction in toluene is independent of the quenching mechanism. The fluorescence quenching of QDs by nitroxide binding is a reversible process.

Awaruite (Ni 3Fe) as a nickel resource—leaching with ammoniacal–ammonium solution containing citrate and thiosulfate

A method was developed for extraction of nickel from ultramafic rocks containing awaruite, an alloy of nickel and iron (nominally Ni 3Fe). The leaching solution contained ammonia, ammonium, citrate and thiosulfate at moderately alkaline pH. Leaching studies were carried out on synthetic Ni 3Fe, josephinite (a naturally occurring material consisting mainly of awaruite from Oregon, USA) and serpentinite containing low levels of awaruite from British Columbia, Canada. In addition to citrate, several other carboxylic acid ligands were also found to be suitable for this process.

A Ru‐Hbpp‐Based Water‐Oxidation Catalyst Anchored on Rutile TiO2

Two organic ligands based on bis-(2-pyridyl)pyrazole (Hbpp) functionalized with a para-methylenebenzoic acid (Hbpp-R(a)) or its ester derivative (Hbpp-R(e)) were prepared and characterized. The ester-functionalized ligand was then used to prepare a series of related dinuclear ruthenium complexes of general formula [Ru(II)2(L-L)(bpp-R(n))(trpy)2](m+) (L-L=mu-Cl, mu-acetato, or (H2O)2; n=e or a; trpy=2,2':6',2''-terpyridine; m=2 or 3). The complexes were characterized in solution by 1D and 2D NMR spectroscopy, UV/Vis spectroscopy, and electrochemical techniques. The [Ru(II)2(mu-Cl)(bpp-R(e))(trpy)2](PF6)(2) complex was further characterized in the solid state by X-ray diffraction. The complexes containing the free carboxylic acid ligand were anchored onto rutile TiO2 and treated with 0.1 M triflic acid solution to generate the homologous water-oxidation catalysts TiO(2)-[Ru(II) (2)(H2O)(2)(bpp-R(a))(trpy)2]2+. This new hybrid material catalytically oxidizes water to molecular oxygen in a heterogeneous manner using Ce(IV) as chemical oxidant. The generation of molecular oxygen is accompanied by the formation of carbon dioxide as well as some leaching of the Ru catalyst.

Assembly and Interfacial Effects in Hybrid Nanostructures of Zinc Oxide and Gold

AbstractGold nanoparticles were linked to ZnO films and nanowires using phosphonic and carboxylic acid ligands. TEM and STEM-HAADF characterization showed that gold nanoparticles modified with both types of ligands anchored on ZnO nanowire surfaces as well as on ZnO films. After removing the ligands from the interface between ZnO nanowires and supported gold nanoparticles, the electric conductivity in the presence of methanol vapor increased by 100 times as compared to the bare ZnO nanowire, which suggested enhanced-catalytic effects due to the hybrid structure. In addition, ZnO/Au nanomaterials were synthesized by linking ZnO nanoparticles and carboxylate-functionalized gold nanoparticles in solution. UV-vis characterization showed both the bandgap absorption from ZnO and the plasmon absorption from gold nanoparticles. Formation of hybrid nanosystems like these using organic ligands as linkers not only can lead to materials with enhanced properties but also minimize the waste of precious elements because the assembly process is an additive, rather than subtractive, process.

Rhodium carbonyl complexes containing pyridine carboxylic acid ligands: Reactivity towards various electrophiles and catalytic activity

The complex [Rh(CO) 2Cl] 2 reacts with two molar equivalent of pyridine carboxylic acids ligands Py-2-COOH( a), Py-3-COOH( b) and Py-4-COOH( c) to yield rhodium(I) dicarbonyl chelate complex [Rh(CO) 2(L /)]( 1a) {L / = η 2-(N,O) coordinated Py-2-COO −( a / )} and non-chelate complexes [Rh(CO) 2ClL //]( 1b,c) {L // = η 1-(N) coordinated Py-3-COOH( b), Py-4-COOH( c)}. The complexes 1 undergo oxidative addition ( OA) reactions with different electrophiles such as CH 3I, C 2H 5I, C 6H 5CH 2Cl and I 2 to give penta coordinated Rh(III) complexes of the types [Rh(CO)(COR n)XL /], { n = 1,2,3; R 1 = CH 3( 2a); R 2 = C 2H 5( 3a); X = I and R 3 = CH 2C 6H 5 ( 4a); X = Cl}, [Rh(CO)I 2L /]( 5a), [Rh(CO)(COR n)ClXL //] {R 1 = CH 3( 6b,c); R 2 = C 2H 5( 7b,c); X = I and R 3 = CH 2C 6H 5 ( 8b,c); X = Cl} and [Rh(CO)ClI 2L //]( 9b,c). The complexes have been characterized by elemental analysis, IR and 1H NMR spectroscopy. Kinetic data for the reaction of 1a–b with CH 3I indicate a first order reaction. The catalytic activity of 1a–c for the carbonylation of methanol to acetic acid and its ester is evaluated and a higher turn over number (TON = 810–1094) is obtained compared with that of the well-known commercial species [Rh(CO) 2I 2] − (TON = 653) at mild reaction conditions (temperature 130 ± 5 °C, pressure 35 ± 5 bar).

Synthesis, crystal structures, and fluorescence properties of six complexes with thiophene derivative carboxylic acid ligand

The crystallization of 2,3-dihydro-thieno[3,4- b][1,4] dioxine-5,7-dicarboxylic acid (H 2tddc) with divalent transitional metal (Co, Ni, Zn, Cd) or with tervalent lanthanide metal (Sm) and with mixed ligand 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (1,10-phen) formed six new complexes: [Co(C 8H 4O 6S) · 3H 2O] ( 1), [Co(C 8H 4O 6)(1,10-phen)(H 2O)] · H 2O ( 2), [Ni(C 8H 4O 6S)(4,4′-bipy)(H 2O)] · 3H 2O ( 3) [Sm(C 8H 4O 6S)(NO 3)(H 2O) 4] · 2H 2O ( 4), [Zn(C 8H 4O 6S)(H 2O) 3] ( 5), and [Cd 2(C 8H 4O 6S) 2(4,4′-bipy) 2] ( 6). The structures of these six crystals have been characterized by single-crystal X-ray diffraction analyses, which revealed that complexes 1, 4, 5 are all one-dimensional chain structures and they self-assemble into three-dimensional super-molecules via the hydrogen bond interactions and π–π stacking interactions, 2 is also a one-dimensional chain structure but still self-assembles into one-dimensional double-chains, the complex 3 has two-dimensional undulating parallelogram grid structure extended along the bc-plane, the crystal of 6 is a 3D threefold interpenetration topology framework with 4 66 38 nodes. The photoluminescent properties of the H 2tddc ligand and the six compounds have been measured in the solid state at room temperature. Free ligand has no luminescence, while its complexes 1, 4, and 6 all exhibit intense photoluminescence which implies that these complexes may be excellent candidates for potential photoactive materials.

Preparation and X‐ray Structures of TiIV Complexes of Bis(carboxylato) Ligands – Formation of Mono‐, Di‐, Tetra‐, and Hexanuclear Complexes with or without OR and μ‐O Ligands

AbstractTreating the amine bis(carboxylato) ligand precursor pyridine‐2,6‐dicarboxylic acid (H2L1) with titanium tetra(isopropoxide) gave the mononuclear octacoordinate complex L12TiIV(dmf)2 (1), in which each carboxylato ligand binds in an η1 fashion and two solvent molecules are also coordinated to the metal. In contrast, employing the diamine bis(carboxylic acid) ligand precursor H2L2 gave a unique hexanuclear TiIV complex [TiIV6(OiPr)16(μ2‐OiPr)4(μ‐L2)2] (2), where L2 = (pyridin‐2‐ylmethyl)amino diacetate. The crystal structure reveals that all TiIV atoms exhibit octahedral geometry, where both carboxylate and isopropoxide groups serve as bridging ligands. Surprisingly, no oxido ligands appear in the structure, which indicates that the complex, obtained at room temp., was not exposed to any traces of water. The diamine bis(carboxylato) ligand coordinates in η2 modes of both carboxyl groups to give a total of six coordination sites. Employing the same ligand with a slight change in reaction conditions, which included heating to 35 °C, led to the formation of two O‐bridged complexes: dinuclear [TiIV2(μ2‐O)(OiPr)2(L2)2] (3) and tetranuclear [TiIV4(μ2‐O)4(L2)4] (4), where each bis(carboxylato) ligand binds to a single Ti center in an η1 fashion, and the only bridging ligands are oxide groups, with Ti–O–Ti angles of 180.0° and 166.6° for 3 and 4, respectively, indicating π interactions in the dinuclear species. Employing a different diamine bis(carboxylato) ligand featuring a sequential connectivity of donor atoms allowed the identification of a mononuclear C2‐symmetrical bis(isopropoxido) complex, L3TiIV(OiPr)2, (5) where L3 = ethylenediamine diacetate. In 5, as opposed to 2 and similarly to 1, 4, and 5, the carboxylato ligand binds in an η1 fashion. Complexes 3, 4, and 5 are all inactive against ovarian OVCAR‐1 and colon HT‐29 cells. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)