Reactions of bis(hexamethylbenzene)iron(0) with carbon monoxide and with unsaturated hydrocarbons

Thermal decomposition of bis(hexamethylbenzene)iron(0) in the presence of carbon monoxide yields a novel carbonyl iron complex, [C₆(CH₃)₆]Fe(CO)₂. The cyclohexadiene complex [C₆(CH₃)₆]Fe(C₆H₈) is obtained from reaction of bis(hexamethylbenzene)iron(0) with either 1,3-cyclohexadiene or benzene, and the yield is much greater in the presence of hydrogen gas. Interaction of bis-(hexamethylbenzene)iron(0) with 2-butyne induces a catalytic cyclotrimerization to give more hexamethylbenzene. Kinetic and isotope distribution studies indicate that the primary step in these reactions is not a direct loss of one ring ligand, but rather an insertion of the iron center into one of the ligand methyl CH bonds, leading to a benzyl hydride complex species. Mechanisms for the subsequent reactions of this iron hydride species are proposed.     

Screening, library-assisted identification and validated quantification of 23 benzodiazepines, flumazenil, zaleplone, zolpidem and zopiclone in plasma by liquid chromatography/mass spectrometry with atmospheric pressure chemical ionization

A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs.     

Strukturen und Molekül-Eigenschaften ladungsgestörter Moleküle. 52. Mitteilung. 2, 3-Diphenylchinoxalin-Radikalanionen in Lösung und im Kristall

Structures and Molecular Properties of Charge-Pertubed Molecules. 2, 3-Diphenylquinoxaline Radical Anions in Solution and in Crystals The Na⊕ and K⊕ radical-ion salts of 2, 3-diphenylquinoxaline seem to be (according to a structural database search) among the first ones of N-heterocyclic radical anions in crystals. The one-electron reduction in aprotic 1, 2-dimethoxyethan (DME) solution at metal mirrors and the crystallization under Ar have been preceded by cyclovoltammetric (CV) and ESR/ENDOR measurement. The first electron insertion at ?1.63 V proves to be reversible, whereas the irreversible second step, which is accompanied by an overcrossing of the CV line, can be rationalized by an ‘ECE-DISP’ mechanism via a dianion redox disproportionation. The ENDOR spectrum resolves four ¹H couplings and allows to simulate the ESR spectrum including the ¹⁴N hyperfine splittings. Both dark-blue single crystals of the radical ion salts $[2,3{\rm - diphenylquinoxaline}^{{.} \ominus} {\rm Met}^ \oplus ({\rm DME})]^.$ show unexpected similarities for Met⊕ = Na⊕, K⊕ despite the 36-pm difference in their ionic radii. The largest structural changes inflicted by the one-electron reduction of the N-heterocyclic molecule are observed in the vicinity of the N-centers bearing the highest effective nuclear charge. The DME-chelated metal cations coordinate at the N electron pairs and form Met⊕(DME)-bridged polymer chains of the radical anion, which are differently ondulated in the Na⊕ and K⊕ radical anion salts. The take-home lesson suggests that many more N-heterocyclic molecules might be analogously reduced under optimized conditions and isolated as single crystals.     

Synthesis of new OBAN's and further studies on positioning of the catalytic group

Two new zinc ion dependent oligonucleotide based artificial nucleases (OBAN's) have been synthesized. These consist of 2'-O-methyl modified RNA oligomers conjugated to 5-amino-2,9-dimethylphenanthroline (neocuproine)via a urea linker. OBAN 4 carries the catalytic group on a linker extending from the C-4 of an internal cytosine moiety. OBAN 5 has two neocuproine units attached, each to linkers extending from the C-5 position of uridine moieties, one placed internally and the other at the at the 5'-end of the oligonucleotide. The key step in the synthesis of the OBAN systems is conjugation of the catalytic group to the respective amino linkers of the modified oligonucleotides. This is achieved by first converting the 5-amino-2,9-dimethylphenanthroline to the phenylcarbamate. The reaction of this neocuproine phenylcarbamate with the oligonucleotide carrying one or two primary aliphatic amines in aqueous buffer (at pH 8.5) leads to nearly quantitative formation of the urea-linked conjugates. Both OBAN systems were found to cleave RNA in the bulged out regions formed from the non-complementary part of the target sequences, in the presence of Zn(II) ions. Differences in efficiency between these and previously reported systems are discussed.     

Electrochemistry of capillary systems with narrow pores. IV. Dialysis potentials

The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes.     

Indications for the Occurrence of Nitric Oxide Synthases in Fungi and Plants and the Involvement in Photoconidiation of Neurospora crassa*

Indications for the occurrence of nitric oxide synthases in Dictyostelium, Neurospora, Phycomyces and the leguminous plant Mucuna hassjoo as well as a physiological role of nitric oxide in Neurospora crassa are demonstrated. An exogenous nitric oxide donor, sodium nitroprus-side, inhibited light-stimulated conidiation in N. crassa. Specific inhibitors of nitric oxide synthase, like the arginine derivatives N^G-nitro-L-arginine (L-NA) and N^G-nitro-L-arginine-methyl ester (L-NAME), enhanced conidiation in darkness and in the light, whereas the stereo-isomer D-NAME was inactive. This communication reports to our knowledge the first time the presence of enzymatic activity of nitric oxide synthase in fungi and a higher plant and an effect of nitric oxide in fungal photophysiology.     

Solvothermale Synthese und Bestimmung der Kristallstrukturen von AgBiI4 und Ag3BiI6

Solvothermal Synthesis and Crystal Structure Determination of AgBiI₄ and Ag₃BiI₆ AgBiI₄ and Ag₃BiI₆ were synthesized by solvothermal reaction from AgI and BiI₃ in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI₄) or hexagonal/trigonal platelets (Ag₃BiI₆). AgBiI₄ crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag₃BiI₆ shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI₄ is explored. AgBiI₄ and Ag₃BiI₆ show close structural relationship, with AgBiI₄ as a variant with a higher degree of order.     

Electrospray ionization ion-trap multistage mass spectrometric study of sodium cationized aldobiuronic and pseudoaldobiuronic acid derivatives

Fragmentation mechanisms of electrospray ionization (ESI) mass spectrometry of aldobiuronic and pseudoaldobiuronic acid derivatives were elucidated by multistage mass spectrometric (MS(n), n = 2-5) measurements of selected ions. Characteristic under the conditions of ESI-MS analysis is the production of alkali metal (Na and K) cationized adducts. The probability the of locations of Na cations in per-O-methylated compounds was proved by quantum chemical calculations, using the Jaguar program. The most probably position of alkali metal attachment is the carboxy group of the methoxycarbonyl C-5 group of the uronic acid unit. Characteristic cleavages vary according the kind of O-derivatization. In most cases they take place on the acidic part of the dimer and at the interglycosidic oxygen atom. As a result, the criteria for the differentiation of aldobiouronic and pseudoaldobiouronic acids derivatives were elucidated.     

Stereoselective synthesis of optically active bicyclic beta-lactam carboxylic acids that target pilus biogenesis in pathogenic bacteria

Optically active bicyclic beta-lactams were synthesized, starting from 2-H-delta 2-thiazolines and Meldrum's acid derivatives. Several methods to accomplish an ester hydrolysis without damaging the beta-lactam framework were investigated. A rapid CsOH saponification of the beta-lactam methyl esters was developed and protonation of the Cs-carboxylates by Amberlite (IR-120 H+) afforded a series of bicyclic beta-lactam carboxylic acids. Moreover, a convenient method for the synthesis of 2-H-delta 2-thiazolinecarboxylic acid methyl ester 2 was developed. Bicyclic beta-lactam carboxylic acids 7a-g and aldehydes 4a-d were screened for their affinity to the bacterial periplasmic chaperone PapD using a surface plasmon resonance technique. beta-Lactams substituted with large acyl substitutents showed better binding to the chaperone than the native C-terminal peptide PapG 8, demonstrating that bicyclic beta-lactams constitute a new class of potential bacterial chaperone inhibitors.     

Gasphasen-Reaktionen. 92. Thermische HCl-Abspaltung aus Alkyldichlorphosphanen (H3C/H)3C?PCl2 zu Phosphaalkenen (H3C/H)2CPCl und Phosphaalkinen (H3C/H)C≡P

Gasphase Reactions. 92 Thermal Elimination of HCl from Alkyldichlorophosphanes (H₃C/H)₃C? PCl₂ to Phosphaalkenes (H₃C/H)₂C?PCl and Phosphaalkines (H₃C/H)C≡P The alkyldichlorophosphanes H₃C? PCl₂, ClH₂? PCl₂, (H₃C)H₂C? PCl₂ and (H₃C)₂HC? PCl₂ split off HCl on heating in a gasflow under reduced pressure. PE spectroscopic gas analysis proves that under these conditions the short-lived phosphaalkenes H₂C?PCl, (H₃C)H₂C?PCl and – catalyzed by [MgCl₂? MgO/SiO₂]_∞ – (H₃C)₂C?PCl as well as the phosphaalkines HC≡P and (H₃C)C≡P are formed, all of which can be isolated by low temperature condensation. Based on the PES ionization patterns recorded and on the MNDO calculations for their assignment, the π_CP multiple bonds are discussed. The presumable pathway of the HCl elimination is rationalized for (H₃C)H₂C? PCl₂ by an approximate MNDO energy hypersurface.