Identification of formylglycine in sulfatases by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

C(alpha)-Formylglycine, the catalytic amino acid residue in the active site of sulfatases, is generated by post-translational modification of a cysteine or serine residue. We describe a highly sensitive procedure for the detection of C(alpha)-formylglycine-containing peptides in tryptic digests of sulfatase proteins. The protocol is based on the formation of hydrazone derivatives of C(alpha)-formylglycine-containing peptides when using dinitrophenylhydrazine as a matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The hydrazone derivatives desorb and ionize with high efficiency and can be detected in the sub-femtomole range. The presence of C(alpha)-formylglycine is indicated by a mass increment of 180.13 u, corresponding to the hydrazone moiety, and also by a unique C-terminal fragment ion, characteristic of sulfatases, that becomes prominent in MALDI post-source decay mass spectra of the hydrazone derivatives.     

Homopolar- and Heteropolar Bond Dissociation Energies and Heats of Formation of Radicals and Ions in the Gas Phase. I. Data on organic molecules

The literature data on heteropolar and homopolar 2-center bond dissociation energies in organic molecules in the gas phase and the corresponding heats of formation of radicals and ions have been critically evaluated. Data for more than 500 bonds are represented in tabular form together with the pertinent literature references. Selected electron affinities and π-bond dissociation energies have also been incorporated. The follow-up paper will discuss some empirical general aspects of these data particularly regarding the effect of structure on the bond dissociation energies.     

Internal rotation and pyramidal inversion in triacylphosphines

MO calculations predict a P-C rotation barrier in triformylphosphine of less than 6 kcal/mol, and an inversion barrier of ca 14 kcal/mol.     

Fluorodiazadiphosphetidine, 12. Mitt.: Reaktionen von Oktafluoro-1,3,2λ6,4λ6-diazoniadiphosphatetidinen

Reaction of (CH₃NHPF₄)₂ with selected organometallic reagents yields (CH₃NPF₃)₂, while reaction with non-nucleophilic bases such as 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-Bis(dimethylamino)naphthalin and with alkali fluorides yields ionic compounds with the diazoniadiphosphatetidine ring as a dianion.     

1,3-Oxazolidin-4-ones. Synthesis and configuration of cis and trans isomers

Mixtures of cis and trans 1,3-oxazolidin-4-ones were obtained by cyclodehydration, in the presence of p-toluenesulfonic acid or boron trifluoride etherate, of lactamide and N-methyl-lactamide with aromatic and aliphatic aldehydes. The products were separated by column (silica) chromatography and their configurations were determined.     

Structure and diffusion in amorphous aluminum silicate: a molecular dynamics computer simulation

The amorphous aluminum silicate (Al2O3)2(SiO2) [AS2] is investigated by means of large scale molecular dynamics computer simulations. We consider fully equilibrated melts in the temperature range 6100 K> or =T> or =2300 K as well as glass configurations that were obtained from cooling runs from T=2300 to 300 K with a cooling rate of about 10(12) K/s. Already at temperatures as high as 4000 K, most of the Al and Si atoms are fourfold coordinated by oxygen atoms. Thus, the structure of AS2 is that of a disordered tetrahedral network. The packing of AlO4 tetrahedra is very different from that of SiO4 tetrahedra in that Al is involved with a relatively high probability in small-membered rings and in triclusters in which an O atom is surrounded by four cations. We find as typical configurations two-membered rings with two Al atoms in which the shared O atoms form a tricluster. On larger length scales, the system shows a microphase separation in which the Al-rich network structure percolates through the SiO2 network. The latter structure gives rise to a prepeak in the static structure factor at a wave number q=0.5 A(-1). A comparison of experimental x-ray data with the results from the simulation shows good agreement for the structure function. The diffusion dynamics in AS2 is found to be much faster than in SiO2. We show that the self-diffusion constants for O and Al are very similar and that they are by a factor of 2-3 larger than the one for Si.     

103Rh-NMR-spektroskopischer Nachweis der gemischten Nonahalogenodirhodate(III), [Rh2ClnBr9–n]3−, n = 0–9

¹⁰³Rh NMR Spectroscopic Evidence of Mixed Nonahalogenodirhodates(III), [Rh₂Cl_nBr_9–n]^3?, n = 0–9 On heating a mixture of the tetrabutylammonium salts (TBA)₃[Rh₂Cl₉] and (TBA)₃[Rh₂Br₉] at 60°C in propylenecarbonate the complete system of the mixed nonahalogenodirhodates(III) [Rh₂Cl_nBr_9–n]^3?, n = 0–9 is formed. In the ¹⁰³Rh nmr spectra 40 different species have been detected, 16 with two equivalent ¹⁰³Rh atoms each resulting in one singlet and 24 with inequivalent ¹⁰³Rh atoms each pair giving two resonances. The signals of the geometric isomeres are not resolved. All 64 expected resonances are really observed. By additional measuring of the ¹⁰³Rh nmr spectra of the fractions n = 0–4 separable by ion exchange chromatography on DEAE cellulose, and utilizing characteristic increments of chemical shifts the complete and unambiguous assignment of all signals is achieved.     

Synthesis of 5-cyclopropyluracil and 5-cyclopropylcytosine by the Pd(0)-catalyzed coupling reaction

5-Cyclopropyluracil and cyclopropylcytosine were prepared by the Pd(0)-catalyzed coupling reaction of 5-bromo-2,4-di(trimethylsilyloxy)pyrimidine and 5-bromo-2,4-O,N-bis-trimethylsilylcytosine with tributylstan-nylcyclopropane. The reactions also gave dehalogenated pyrimidine bases as by-products. Attempts to use 2,4-O,N-bis-trimethylsilyl-5-iodocytosine as the halide gave complete dehalogenation.     

(PPh4)2[WO2Cl3]2 · 2 CH2Cl2: Synthese,Schwingungsspektrum und Kristallstruktur

(PPh₄)₂[WO₂Cl₃]₂ · 2 CH₂Cl₂. Synthesis, Vibrational Spectrum, and Crystal Structure Depending on the stoichiometry and the solvent, dichloromethane or 1.2-dichloroethane, WO₂Cl₂ reacts with tetraphenylphosphonium chloride affording (PPh₄)₂[WO₂Cl₄] or (PPh₄)₂[WO₂Cl₃]₂, respectively. Both compounds are easily soluble in dichloromethane, from which they can be crystallized under incorporation of two molecules CH₂Cl₂ per formula unit. The crystalline compounds have been characterized by their IR and Raman spectra. According to the X-ray crystal structure analysis, (PPh₄)₂[WO₂Cl₃]₂ · 2 CH₂Cl₂ crystallizes in the triclinic space group P1 with one formula unit per unit cell (986 independent observed reflexions, R = 0.061). Lattice constants: a = 1100.2, b = 1116.9, c = 1238.4 pm, = 69.40, = 80.46 and = 85.62°. The crystals consist of PPh₄^⊕ ions, centrosymmetric [WO₂Cl₃]₂^2? anions and CH₂Cl₂ molecules. In the anions, the tungsten atoms are linked via two oxo bridges with WO distances of 184 and 252 pm. The distorted octahedral coordination around each tungsten atom is completed by three terminal chloro and one terminal oxo ligand (WO bond length 166 pm), the latter being in trans position to the longer WO bridging bond. (PPh₄)₂[WO₂Cl₄] · 2 CH₂Cl₂ also forms triclinic crystals that are isotypic with (PPh₄)₂[WOCl₅] · 2 CH₂Cl₂ and in which the anions must have orientational disorder.     

Total synthesis of (±)-Δ9(12)-capnellene via iterative intramolecular type-I-“Magnesium-ene” reactions

The marine triquinane sesquiterpene Δ⁹(¹²)-capnellene ($\text{1}$) was synthesised from 2,2,5-trimethyl-5-hexenal ($\text{2}$) by a sequence of all synthetic operations in 5% overall yield. The key steps 3 → 4 → 5 → 6 involve two intramolecular type-I-“Mg-ene” processes.