A new dimension in multinuclear metallocene complexes.
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Journal Article↗
Biomedical subjects
Matthias Wagner
Publications and source records attributed to Matthias Wagner.
Hydroquinone-bridged dinuclear Cu(II) complexes and single-crystalline Cu(II) coordination polymers.
Cationic dinuclear Cu(II) complexes 3 and 4 have been prepared using the novel hydroquinone-based imine chelators 2,5-((i)Pr(2)NCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (1) and 2,5-(pyCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (2), respectively (py = 2-pyridyl). X-Ray quality crystals of both complexes were grown from their DMF solutions. The sterically more encumbered compound crystallizes in the form of discrete dinuclear entities with Cu(II) centres in a distorted square-planar ligand environment (one coordination site is occupied by a DMF molecule). The pyridyl derivative 4 features dinuclear hydroquinone-bridged subunits similar to 3. However, the Cu(II) ions are now six-coordinate with two DMF molecules at an axial and an equatorial position of a Jahn-Teller-distorted octahedron. Moreover, the dinuclear subunits are no longer isolated but linked with each other via bridging hydroquinone oxygen atoms which occupy the second apical position of each octahedron. The structure suggests that the magnetic properties of the resulting coordination polymer of 4 could be described by a model valid for dimerized spin chains. As a result of this analysis the antiferromagnetic coupling constants J(1)/k(B) = 9.9 K (intradimer) and J(2)/k(B) = 0.9 K (interdimer) are obtained. Both in 3 and in 4, the hydroquinone --> semiquinone transition of the central bridging unit (E degrees ' = + 0.57 V, 3; E degrees ' = + 0.51 V, 4; DMF; vs. SCE) displays features of chemical reversibility. In the case of , reduction of Cu(II) centres requires a peak potential of E(p) = - 0.42 V.
Journal Article↗
Synaptic amplifier of inflammatory pain in the spinal dorsal horn.
Inflammation and trauma lead to enhanced pain sensitivity (hyperalgesia), which is in part due to altered sensory processing in the spinal cord. The synaptic hypothesis of hyperalgesia, which postulates that hyperalgesia is induced by the activity-dependent long-term potentiation (LTP) in the spinal cord, has been challenged, because in previous studies of pain pathways, LTP was experimentally induced by nerve stimulation at high frequencies ( approximately 100 hertz). This does not, however, resemble the real low-frequency afferent barrage that occurs during inflammation. We identified a synaptic amplifier at the origin of an ascending pain pathway that is switched-on by low-level activity in nociceptive nerve fibers. This model integrates known signal transduction pathways of hyperalgesia without contradiction.
Animals↗
Modular approach to tridentate N,O,N' ligands using pyrazolylborate chemistry.
Two anionic tridentate N,O,N' chelators, [pz(Ph)B(mu-pz)(mu-O)B(Ph)pz](-) (3(-)) and [pz(Ph)(Ph)B(mu-pz)(mu-O)B(Ph)pz(Ph)](-) (4(-)), as well as the corresponding complexes [Fe(3)(py)Cl], [Fe(3)Cl(2)] and [Cu(3)Cl], have been synthesised and structurally characterised by X-ray crystallography (pz: pyrazolyl, pz(Ph): 3-phenylpyrazolyl, py: pyridine). Since our synthesis approach takes advantage of the highly modular pyrazolylborate chemistry, inexpensive and relatively resistant N,O,N' ligands of varying steric demand are readily accessible. The complexes [Fe(3)(py)Cl] and [Fe(3)Cl(2)] possess a distorted trigonal-bipyramidal configuration with the pyrazolyl rings occupying equatorial positions and the oxygen donor being located at an apical position. The complex [Cu(3)Cl] crystallises as chloro-bridged dimers featuring Cu(II) ions with ligand environments that are intermediate between a square-planar and a trigonal-bipyramidal geometry.
Journal Article↗
The pentanuclear Fe(II) cluster [(C5H4)6Fe5]2-: bringing together ferrocene sandwiches and homoleptic Fe(II)-cyclopentadienyl sigma-complexes.
Reaction of [(fc)3(Li)6.(TMEDA)2] with FeCl2 gives the pentanuclear iron complex [(fc)3(Fe)2(Li)2.(TMEDA)2] featuring two ferra[1]ferrocenophane moieties bridged by a 1,1'-ferrocenediyl unit; the non-ferrocene Fe(II) ions are tetra-coordinate and adopt a high-spin state.
Journal Article↗
A DSC and Raman spectroscopy study on the effect of PAMAM dendrimer on DPPC model lipid membranes.
The interaction between PAMAM (polyamidoamine) dendrimer generation 4 (G4) and 3,5 (G3,5) with model lipid membranes composed of dipalmytoylphosphatidylcholine (DPPC) has been investigated. Differential scanning calorimetry (DSC) and Raman spectroscopy were applied to assess the thermodynamic changes caused by PAMAM G4 and G3,5 and to specify the exact location of these dendrimers into the DPPC lipid bilayer. DSC thermograms indicated that the maximum percentages of PAMAM G4 and of G3,5 that can be incorporated in the DPPC membrane without deranging its integrity were 5% and 3%, respectively. The Raman intensity ratios I(2935/2880), I(2844/2880) and I(1090/1130) cm(-1) showed the degree of the fluidity of the lipid bilayer, while the absorption at 715 cm(-1) showed a strong interaction of PAMAM G4 and G3,5 with the polar head group of phospholipid. The results showed that the incorporation of the PAMAM G4 and G3,5 dendrimers in DPPC bilayers causes a concentration dependent increase of the membrane fluidity and that the bilayers interact strongly with both the lipophilic part and the polar head group of the phospholipids. Due to the current weak knowledge relating to the mechanism(s) under which dendrimers interact with lipidic membranes and transport through cells, these results may justify the tendency of dendrimers to disrupt biological membranes. The findings from this study could also prove helpful to rationally design new liposomal drug carriers for bioactive molecules by combining dendrimeric and liposomal technologies.
1,2-Dipalmitoylphosphatidylcholine↗
Mono-, di-, and oligonuclear complexes of Cu(II) ions and p-hydroquinone ligands: syntheses, electrochemical properties, and magnetic behavior.
Four highly soluble square-planar Cu(II) and Ni(II) complexes of siloxy-salens (2SiCu, 2SiNi) and hydroxy-salens (2Cu, 2Ni) have been synthesized. An X-ray crystal structure analysis was performed on 2SiCu, 2SiNi, and 2Ni. The compounds have been investigated by cyclic voltammetry, UV-vis-NIR spectroelectrochemistry, and EPR spectroscopy. According to these results, the monooxidized species [2SiCu]+ and [2SiNi]+ are to be classified as Robin-Day class II and III systems, respectively. Magnetic measurements on the dinuclear (PMDTA)Cu(II) complex 1Cu2 x (PF6)2 with deprotonated 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)-benzene (1) linker revealed antiferromagnetic coupling between the two Cu(II) ions thereby resulting in an isolated dimer compound. Coordination polymers [1Cu]n(H2O)(2n) of Cu(II) ions and bridging p-hydroquinone linkers were obtained from CuSO4 x 5 H2O and 1,4-dihydroxy-2,5-bis(pyrazol-1-yl)benzene. X-ray crystallography revealed linear chains running along the crystallographic a-direction and stacked along the b-axis. Within these chains, the Cu(II) ions are coordinated by two pyrazolyl nitrogen atoms and two p-hydroquinone oxygen atoms in a square-planar fashion.
Copper↗
A synthetic route to borylene-bridged poly(ferrocenylene)s.
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Journal Article↗
www.tnt-radiology.de: Teach and be taught radiology: implementation of a web-based training program based on user preferences as determined by survery.
RATIONALE AND OBJECTIVES: To create a Web-based training program addressing the needs of a large, heterogeneous audience of users. MATERIALS AND METHODS: We defined our target group as consisting of medical professionals who teach radiology, or who, by their own perception, would benefit from improving their radiologic image interpretation skills. We interviewed 483 members of this group, eliciting their preferences with regard to layout, interactivity, contents, and other categories (11 in total). Considering majority preferences as recommendations and using the help of a special interest group of medical students, we assembled 500 teaching cases over a 1-year period into an interactive training program and made it available on the World Wide Web. RESULTS: Important preferences expressed by majorities of interviewees were: high levels of interactivity, clear layout, intuitive usability, short page load times, permissibility of saving content locally, cost-free access, consideration of user input in the site development. To our knowledge, our web program TNT-Radiology, accessible at , is the first to implement all of these recommendations simultaneously. CONCLUSIONS: We have created a Web-based program usable for teaching and learning radiologic image interpretation that meets the needs of a heterogeneous target audience to an unprecedented extent.
Computer-Assisted Instruction↗
A chloro-bridged dimanganese complex and an oxo-bridged dititanium complex of a ditopic bis(pyrazol-1-yl)borate ligand.
The synthesis and crystal structure analysis of the ditopic p-phenylene-bridged bis(pyrazol-1-yl)borate [[p-C6H4(Bpz2tBu)2]Li2] (LLi2; pz=pyrazol-1-yl) is described. A salt metathesis reaction between LLi2 and MnCl2 in THF leads to the dinuclear complex [L[Mn(THF)]2(mu-Cl)2] featuring a central diamond MnII-(mu-Cl)2-MnII core (X-ray crystal structure analysis). Treatment of LLi2 with 2 equiv of [Ti(NMe2)3Cl] gives the dinuclear titanium compound [L[Ti(NMe2)3]2]. Upon reaction of LLi2 with [Ti(NMe2)2Cl2] and water, the mu-oxo-bridged dititanium species [L[Ti(NMe2)Cl]2(mu-O)] is obtained in excellent yield (X-ray crystal structure analysis).
Boron Compounds↗
Synthesis and crystal structure of [tBu3SiPAg2]8: a novel Ag16-cluster featuring a remarkable symmetrical structure.
The synthesis of [tBu3SiPAg2]8 which features an Ag16-cluster in the solid state was achieved by metathesis reaction of AgOCN with tBu3SiPNa2.
Journal Article↗
A joint experimental and theoretical study of cation-pi interactions: multiple-decker sandwich complexes of ferrocene with alkali metal ions (Li+, Na+, K+, Rb+, Cs+).
A systematic study of cation-pi interactions between alkali metal ions and the cyclopentadienyl ring of ferrocene is presented. The alkali metal (Li+, Na+, K+, Rb+, Cs+) salts of the ditopic mono(pyrazol-1-yl)borate ligand [1,1'-fc(BMe2pz)2]2- crystallize from dimethoxyethane as multiple-decker sandwich complexes with the M+ ions bound to the pi faces of the ferrocene cyclopentadienyl rings in an eta5 manner (fc = (C5H4)2Fe; pz = pyrazolyl). X-ray crystallography of the lithium complex reveals discrete trimetallic entities with each lithium ion being coordinated by only one cyclopentadienyl ring. The sodium salt forms polyanionic zigzag chains where each Na+ ion bridges the cyclopentadienyl rings of two ferrocene moieties. Linear columns [-CpR-Fe-CpR-M+-CpR-Fe-CpR-M+-](infinity) (R = [-BMe2pz]-) are established by the K+, Rb+, and Cs+ derivatives in the solid state. According to DFT calculations, the binding enthalpies of M+-eta5(ferrocene) model complexes are about 20% higher as compared to the corresponding M+-eta6(benzene) aggregates when M+ = Li+ or Na+. For K+ and Rb+, the degree of cation-pi interaction with both aromatics is about the same. The binding sequence along the M+-eta5(ferrocene) series follows a classical electrostatic trend with the smaller ions being more tightly bound.
Journal Article↗
Solvent-free methylthiomethyllithium [LiCH2SMe]infinity: solid state structure and thermal decomposition.
Solvent-free [LiCH2SMe]infinity forms a layer structure consisting of four- (Li2C2), five- (Li2CS2), and six-membered (Li2C2S2) rings in the solid state; the compound violently explodes upon heating to T=160+/-5 degrees C under an argon atmosphere.
Hot Temperature↗
Silylchalcogenolates MESiR(t)Bu(2) (M = Na, Cu, Zn, Fe; E = S, Se, Te; R = tBu, Ph) and disilyldichalcogenides tBu2RSiE-ESiRtBu2 (E = S, Se, Te; R = tBu, Ph): synthesis, properties, and structures.
The sodium silyl chalcogenolates NaESiR(t)Bu(2) (R = Ph, (t)Bu; E = S, Se, Te), accessible by the nucleophilic degradation of S, Se, or Te by the sodium silanides NaSiR(t)Bu(2) (R = Ph, (t)Bu), have been characterized by X-ray structure analysis. Protonolysis of the sodium silyl chalcogenolates yields the corresponding chalcogenols. The Cu and Zn chalcogenolates, [Cu(SSiPh(t)Bu(2))](4) and [ZnCl(SSi(t)Bu(3))(THF)](2), have been synthesized by metathesis reactions of CuCl with NaSSiPh(t)Bu(2) and of ZnCl(2) with NaSSi(t)Bu(3), respectively. The solid-state structures of the transition metal thiolates have been determined. The compounds (t)Bu(2)RSiE-ESiR(t)Bu(2) (R = Ph, (t)Bu; E = S, Se, Te) are accessible via air oxidation. With the exception of (t)Bu(3)SiS-SSi(t)Bu(3), these compounds were analyzed using X-ray crystallography and represent the first structurally characterized silylated heavy dichalcogenides. Oxidative addition of (t)Bu(3)SiTe-TeSi(t)Bu(3) to Fe(CO)(5) yields [Fe(TeSi(t)Bu(3))(CO)(3)](2), which has also been structurally characterized.
Journal Article↗
Congenital anomalies of the coronary arteries: imaging with contrast-enhanced, multidetector computed tomography.
The objective of this study is to evaluate multidetector CT (MDCT) in detecting and characterizing anomalous coronary arteries. Forty-four patients with anomalies of the coronaries were selected from a total of 1758 individuals examined with ECG-gated 4- and 16-row MDCT including thinMIP, MPR and VRT post-processing. Twenty-eight patients showed origin and course anomalies of the central coronary segments, and in this subgroup 13 were judged as "malignant" because of interarterial courses between the aortic root and the pulmonary trunk, either of the right coronary artery (n=11) or the left coronary artery (n=2). Twelve non-hemodynamic anomalies were found, affecting the coronary origins only (n=10) or the peripheral vessels courses (n=2). Four arteriovenous fistulas were present, all of them with complex arterial feeders. Regardless of vessel anatomy, coronary opacification was always possible by means of the systemic contrast agent, and the aberrant coronary arteries were visualized synoptically in direct relation to the great mediastinal vessels. In contrast to MDCT, selective cannulation and final diagnosis was possible in only 11 of the 20 catheter angiograms performed (accuracy of 55.0%). In conclusion, its non-invasiveness and precise visualization makes MDCT the standard of reference for evaluating anomalous coronary arteries.
Adult↗
C5H4-BR2 bending in ferrocenylboranes: a delocalized through-space interaction between iron and boron.
A comparison of the molecular structures of mono-, di- and tetraborylated ferrocenes [Fc{B(R(1))(R(2))}] (R(1)/R(2)=Br/Br, Br/Fc, Br/Me, Me/Me, Me/OH, OMe/OMe), 1,1'-[fc{B(R(1))(R(2))}(2)] (R(1)/R(2)=Br/Br, Br/Me, OMe/OMe), and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] revealed the boryl substituent(s) to be bent out of the Cp ring plane towards the iron center. The corresponding dip angle alpha* decreases with decreasing Lewis acidity of the boron atom and with increasing degree of borylation at the ferrocene core. This trend is well reproduced by DFT calculations (including [FcBH(2)], not yet accessible experimentally). A Bader analysis of the electron density topology of [FcBH(2)] (alpha*=26.5 degrees ; BP86/TZVP) clearly showed that there is no direct iron-boron bonding in this compound. Instead, strongly delocalized orbital interactions have been identified that involve the boron p orbital, C(ipso) of the adjacent Cp ring, d orbitals at iron, and a through-space interaction with the second Cp ring. A second important factor is attractive electrostatic interactions, which are enhanced upon ligand bending. Cyclic voltammetric measurements on the series [FcBMe(2)], 1,1'-[fc(BMe(2))(2)], and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] indicate a substantial anodic shift in the oxidation potential of the central iron atom upon introduction of BMe(2) substituents. Addition of 4-dimethylaminopyridine (DMAP) does not just counterbalance this effect, but leads to a cathodic shift of the Fe(II)/Fe(III) redox transition far beyond the half-wave potential of parent ferrocene. In the Mossbauer spectra, a continuous decrease in the quadrupole splitting (QS) is observed upon going from parent ferrocene to [FcBMe(2)], to 1,1'-[fc(BMe(2))(2)], and to 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)]. In contrast, no significant differences are found between the QS values of ferrocene, [Fc(BMe(2)-DMAP)], and 1,1'-[fc(BMe(2)-DMAP)(2)].
Journal Article↗
COMPARE/Radiology, an interactive Web-based radiology teaching program evaluation of user response.
RATIONALE AND OBJECTIVES: The aim of this study is to assess user benefits of COMPARE/Radiology, a highly interactive World Wide Web-based training program for radiology, as perceived by its users. MATERIALS AND METHODS: COMPARE/Radiology (http://www.idr.med.uni-erlangen.de/compare.htm), an interactive training program based on 244 teaching cases, was created by the authors and made publicly available on the Internet. An anonymous survey was conducted among users to investigate the composition of the program's user base and assess the acceptance of the training program. In parallel, Web access data were collected and analyzed using descriptive statistics. RESULTS: The group of responding users (n = 1370) consisted of 201 preclinical medical students (14.7%), 314 clinical medical students (22.9%), 359 residents in radiology (26.2%), and 205 users of other professions (14.9%). A majority of respondents (1230; 89%) rated the interactivity of COMPARE/Radiology as good or excellent. Many respondents use COMPARE/Radiology for self-study (971; 70%) and for teaching others (600; 43%). Web access statistics show an increase in number of site visits from 1248 in December 2002 to 4651 in April 2004. CONCLUSION: Users appreciate the benefits of COMPARE/Radiology. The interactive instructional design was rated positively by responding users. The popularity of the site is growing, evidenced by the number of network accesses during the observation period.
Computer-Assisted Instruction↗
Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges.
Dinuclear and trinuclear ferrocene complexes {[Fc2BMe2]Li, [Fc-BMe2-fc-BMe2-Fc]Li2, Fc2B(pyind), [Fc2B(bipy)]PF6, [Fc-B(bipy)-fc-B(bipy)-Fc](PF6)2} bearing anionic, uncharged, and cationic four-coordinate boron bridges have been synthesized (Fc: ferrocenyl; fc: 1,1'-ferrocenylene; pyind: 5-fluoro-2-(2'-pyridyl)indolyl; bipy: 2,2'-bipyridyl). The molecular structures of [Fc2BMe2]Li(12-crown-4)2, [Fc-BMe2-fc-BMe2-Fc](Li(12-crown-4)2)2, Fc2B(pyind), and [Fc2B(bipy)]PF6 were determined by X-ray crystallography. The anionic aggregates [Fc2BMe2]- and [Fc-BMe2-fc-BMe2-Fc]2- are very sensitive to air and moisture whereas bromide salts of their cationic counterparts [Fc(2)B(bipy)]+ and [Fc-B(bipy)-fc-B(bipy)-Fc]2+ may be dissolved in water without decomposition. Cyclic voltammograms of the diferrocene species show two well-resolved one-electron transitions separated by 0.21 V ([Fc2BMe2]Li; Eo' = -0.43 V, -0.64 V; vs. FcH/FcH+), 0.18 V (Fc2B(pyind); Eo' = -0.03 V, -0.21 V), and 0.16 V ([Fc2B(bipy)]PF6; Eo' = +0.23 V, +0.07 V), which indicates electronic interactions between the two ferrocenyl substituents. Two redox waves with an intensity ratio of 1:2 are observed in the cyclic voltammograms of the trinuclear derivatives [Fc-BMe2-fc-BMe2-Fc]Li2 and [Fc-B(bipy)-fc-B(bipy)-Fc](PF6)2. In the case of the BMe(2)-bridged species, the electrochemically unique central ferrocenylene unit is oxidized at a much more cathodic potential value (Eo' = -1.21 V) than the two terminal ferrocenyl substituents (Eo' = -0.51 V). The opposite is true in the case of the B(bipy)-bridged trimer where oxidation of the terminal ferrocenyl groups (Eo' = +0.03 V) precedes oxidation of the internal iron atom (Eo' = +0.26 V). The Fe(II)/Fe(III) redox potentials of the mono- and dianionic species differ to a much larger extent from the redox potential of parent ferrocene (Eo' = 0 V) than the Eo' values of the corresponding mono- and dicationic derivatives. Apart from electrostatic interactions, the electrochemical properties of BMe2- and B(bipy)-bridged oligoferrocenes are determined by the pronounced positive inductive effect of triorganoborate substituents together with positive sigma/pi* hyperconjugation on the one hand and ferrocene-to-B(bipy) charge transfer on the other.
Journal Article↗