The rate of the reactions of C2O radicals with H and H2

The rate constants for the reactions C₂O + H → products (1) and C₂O + H₂ → products (2) have been determined at room temperature by means of laser-induced fluorescence detection of C₂O radicals, generated either by the KrF excimer laser photolysis Of C₃O₂, or by the reaction of C₃O₂ with O atoms. Values of k₁ = (3.7 ± 1.0) × 10^?11 cm³ s^?1 and k₂ = (7 ± 3) × 10^?13 cm³ s^?1 were obtained.     

Photochemische Reaktionen. 68. Mitteilung. Die Photoisomerisierung von α,β-ungesättigten γ,δ-Epoxyketonen: 9α, 10α- und 9β, 10β-Oxido-3-oxo-17β-acetoxy-Δ4-östren

Irradiation in the n→π* absorption band of the α,β-unsaturated γ,δ-epoxyketone 5 in ethanol at ?65° exclusively afforded the rearranged ene-dione 13 , whereas at + 24° under otherwise unchanged reaction conditions or upon triplet sensitization with Michler's ketone and with acetophenone at + 24° essentially identical mixtures of 13 (major product), 14 , and 15 were obtained. Selective π→π* excitation of 5 at ?78° and + 24° led to similar product patterns. The 9β,10β-epimeric epoxyketone 7 selectively isomerized to 14 and 15 at + 24° and n → π* or π → π* excitation. Neither the epoxyketones 5 and 7 nor the photoproducts 13–15 were photochemically interconverted. In separate photolyses each of the latter gave the double bond isomers 16 , 18 , and 19 , respectively. Cleavage of 13 to the dienone aldehyde 17 competed with the double bond shift ( → 16 ) when photolyzed in alcoholic solvents instead of benzene. The selective transformations 5 → 13 (at ?65° and n → π* excitation) and 7 → 14 + 15 are attributed to stereoelectronic factors facilitating the skeletal rearrangements of the diradicals 53 and 55 , the likely primary photoproducts resulting from epoxide cleavage in the triplet-excited compounds 5 and 7 , via the transition states 54 , 56 , and 57 . The loss of selectivity in product formation from 5 at higher temperature and n → π* excitation or triplet sensitization is explicable in terms of radical dissociation into 58 and 59 increasingly participating at the secondary thermal transformations of 53 . The similar effect of π → π* excitation even at ?78° indicates that some of the π,π* singlet energy may become available as thermal activation energy. It is further suggested that the considerably lesser ring strain in 14 and 15 , as compared with 13 , is responsible that selectivity in product formation from 7 is maintained also at +24° and at π → π* excitation.     

Sequencing of sulfonic acid derivatized peptides by electrospray mass spectrometry

We report the application of nanoelectrospray ionization tandem mass spectrometry (nES-MS/MS) and capillary LC/microelectrospray MS/MS (cLC/&mgr;ES-MS/MS) for sequencing sulfonic acid derivatized tryptic peptides. These derivatives were specifically prepared to facilitate low-energy charge-site-initiated fragmentation of C-terminal arginine-containing peptides, and to enhance the selective detection of a single series of y-type fragment ions. Both singly and doubly protonated peptides were analyzed by MS/MS and the results were compared with those from their derivatized counterparts. Model peptides and peptides from tryptic digests of gel-isolated proteins were analyzed. Derivatized singly protonated peptides fragment in the same way by nES-MS/MS as they do by post-source decay matrix-assisted laser desorption/ionization mass spectrometry (PSD-MALDI-MS). They produce fragment ion spectra dominated by y-ions, and the simplified spectra are readily interpreted de novo. Doubly protonated peptides fragment in much the same way as their non-derivatized doubly protonated counterparts. The fragmentation of doubly protonated derivatives is especially useful for sequencing peptides that possess a proline residue near the N-terminus of the molecule. The singly protonated forms of these proline-containing derivatives often show enhanced fragmentation on the N-terminal side of the proline and considerably reduced fragmentation on the C-terminal side. In addition, sulfonic acid derivatization increases the in-source fragmentation of arginine-containing peptides. This could be useful for sequence verification and sequence tagging for use in single stage mass spectrometry. Copyright 2000 John Wiley & Sons, Ltd.     

Binding N2, N2H2, N2H4, and NH3 to transition-metal sulfur sites: modeling potential intermediates of biological N2 fixation

In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.     

Synthesis and stereochemical assignment of 7-arylidene and 7-heteroarylidene morphinan-6-ones

A number of (E)-7-arylidenenaltrexones were synthesized by azeotropic distillation of water from a benzene solution of naltrexone and an aromatic aldehyde (benzaldehyde, 4-chloro- and 4-fluorobenzaldehyde, 3-and 4-pyridinecarboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde) using piperidine as a catalyst. In addition, (E)-7-benzylidenenaloxone was prepared by the previously published Claisen-Schmidt condensation using sodium hydroxide in methanol. The stereochemistry of these arylidene derivatives 3–9 was determined to be (E) by means of nuclear Overhauser enhancement experiments. The ¹³C nmr spectra of (E)- 3–9 are recorded in deuteriochloroform and those of the hydrochlorides in deuteriodimethyl sulfoxide.     

Recent discoveries on the structure of iodine(iii) reagents and their use in cross-nucleophile coupling

This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, in particular as pertains to their ability to promote the selective coupling of two nucleophilic species via 2e⁻ oxidation.

This perspective article discusses structural features of iodine(iii) compounds as a prelude to presenting their use as umpolung reagents, to promote the selective coupling of two nucleophilic species via 2e⁻ oxidation.     

Structure and Stereochemistry of New Sesquiterpene Esters from Echinacea purpurea (L.) MOENCH. (Preliminary communication)

The structure elucidation of four new constituents from the roots of Echinacea purpurea is described. They are shown to be cinnamoyl esters of sesquiterpene alcohols with a germacrane or a guaiane skeleton. First pharmacological results indicate immunological activities.     

EXAFS Spectroscopy of the Alkoxide Precursor Zr(O n Bu)4 and its Modification in Solution

Summary. The molecular structure of the transition metal alkoxide Zr(OⁿBu)₄ in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy. Zr(OⁿBu)₄ dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand. In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the structural models is given in terms of possible alternatives and errors within the EXAFS analysis.     

Dithiol proteins as guardians of the intracellular redox milieu in parasites: old and new drug targets in trypanosomes and malaria-causing plasmodia

Parasitic diseases such as sleeping sickness, Chagas' heart disease, and malaria are major health problems in poverty-stricken areas. Antiparasitic drugs that are not only active but also affordable and readily available are urgently required. One approach to finding new drugs and rediscovering old ones is based on enzyme inhibitors that paralyze antioxidant systems in the pathogens. These antioxidant ensembles are essential to the parasites as they are attacked in the human host by strong oxidants such as peroxynitrite, hypochlorite, and H2O2. The pathogen-protecting system consists of some 20 thiol and dithiol proteins, which buffer the intraparasitic redox milieu at a potential of -250 mV. In trypanosomes and leishmania the network is centered around the unique dithiol trypanothione (N1,N8-bis(glutathionyl)spermidine). In contrast, malaria parasites have a more conservative dual antioxidative system based on glutathione and thioredoxin. Inhibitors of antioxidant enzymes such as trypanothione reductase are, indeed, parasiticidal but they can also delay or prevent resistance against a number of other antiparasitic drugs.     

Growth and properties of particulate Fe films vapor deposited in UHV on planar alumina substrates

An integrated experimental approach was used to prepare and characterize well-defined particulate deposits of Fe on a variety of planar Al₂O₃ supports. The Fe particles were vapor deposited in UHV on in-situ cleaned and characterized amorphous and single crystal alumina supports at controlled substrate temperatures and deposition rates. Integrated support and deposit properties were monitored in-situ by AES, XPS, and LEED; particle number densities and sizes were monitored by standard TEM. It was found thata) metal exposure is an insufficient and often misleading measure of particle size when the support surface properties are unknown or poorly controlled,b) judicious combination of depostion temperature and impingement flux lead to size- and number density-controlled particulate deposits of good thermal stability, which can be improved by annealing. Preliminary results of XPS and of CO-TPD and H₂-TPD measurements exhibiting particle size effects are also reported.