Inhibitors of biotin biosynthesis as potential herbicides

Isosteric derivatives and analogues of the 7-keto-8-aminopelargonic acid (KAPA), 7,8-diaminopelargonic acid (DAPA) and desthiobiotin (DTB) vitamer intermediates involved in the biosynthetic pathway of biotin were prepared and evaluated as potential herbicides. The most active compound was desmethyl-KAPA which displayed a GR₅₀ (concentration of the active compound that causes a 50% growth inhibition) value of 8 ppm, where values <50 ppm are considered herbicidal. Other KAPA analogs where the terminal Me group was replaced by bulkier substituents such as Et, i-Pr and HOCH₂ showed moderate activity.     

Unusual dealkylations and rearrangements in aromatic nucleophilic substitution

The reaction of 2,4-dinitrohalobenzenes with di-isopropylamine produces mainly N-(2,4-dinitrophenyl)-isopropylamine and N-(2,4-dinitrophenyl)-n-propylamine instead of the expected straightforward substitution product. Dealkylations are also observed in the reactions with isopropylcyclohexylamine and dicyclohexylamine. A carbanionic mechanism is proposed.     

Topological hochschild homology of extensions of ?/p? by polynomials, and of ?[x]/(xn) and ?[x]/(xn?1)

Topological Hochschild homology is calculated for the rings /p[x]/(f(x)) (where p is prime and f(x) /p[x] any polynomial), [x]/(x ⁿ) and [x]/(x ⁿ–1). A spectral sequence argument is used for calculating the homology of the topological Hochschild homology spectrum, from which its stable homotopy structure can be read off since the spectrum is known for a priori reasons to be a restricted product of Eilenberg-MacLane spectra.     

A Convenient Synthesis of Chiral Oxazolidin-2-Ones and Thiazolidin-2-Ones and an Improved Preparation of Triphosgene

Oxazolidin-2-ones and thiazolidin-2-one are conveniently prepared by condensation of L-serine, L-threonine and L-cysteine, respectively with triphosgene. The corresponding methyl esters may be subsequently obtained by quenching the reaction mixture with methanol, without prior need for the isolation of the free acids. An improved procedure for preparation of triphosgene using an internal cooling system is described.     

Isosteres of Natural Phosphates. Methylene and Hydroxyrnethylene Analogues of Tyrosine O-Phosphate

Abstract

The ability of phosphonic acid analogues isosteric with natural phosphate esters to Serve as inhibitors of enzymatic phosphate hydrolysis has been documented in a wide variety of systems.¹ The use of such an analogue in place of the natural phosphate ester provides a functionality which the enzyme may not be able to distinguish from the natural ester, but which is incapable of being hydrolyzed. In some instances the use of hydroxymethylene analogues has resulted in a greater degree of recognition, and resultant inhibition of hydrolytic activity, than the simple methylene analogues.² On this basis, the methylene and hydroxymethylene analogues of tyrosine O-phosphate appear to be reasonable candidates to Serve as inhibitors for phosphoprotein phosphatases and alkaline phosphatase, and as probes for biological mechanisms.     

Hydrogen‐bonded nucleophile effects in ANS: the reactions of 1‐chloro and 1‐fluoro‐2,4‐dinitrobenzene with 2‐guanidinobenzimidazole, 1‐(2‐aminoethyl)piperidine and N‐(3‐aminopropyl)morpholine in aprotic solvents

The kinetics of the reactions of 2,4‐dinitrofluorobenzene (DNFB) and 2,4‐dinitrochlorobenzene (DNClB) with 2‐guanidinobenzimidazole (2‐GB) at 40 ± 0.2 °C in dimethylsulphoxide (DMSO), toluene, and in toluene–DMSO mixtures, and with 1‐(2‐aminoethyl)piperidine (2‐AEPip) and N‐(3‐aminopropyl)morpholine (3‐APMo) in toluene at 25 ± 0.2 °C were studied under pseudo first‐order conditions. For the reactions of 2‐GB carried out in pure DMSO, the second‐order rate coefficients were independent of the amine concentration. In contrast, the reactions of 2‐GB with DNFB in toluene, showed a kinetic behaviour consistent with a base‐catalysed decomposition of the zwitterionic intermediate. These results suggest an intramolecular H‐bonding of 2‐GB in toluene, which is not present in DMSO. To confirm this interpretation the reactions were studied in DMSO–toluene mixtures. Small amounts of DMSO produce significant increase in rate that is not expected on the basis of the classical effect of a dipolar aprotic medium; the effect is consistent with the formation of a nucleophile/co‐solvent mixed aggregate. For the reactions of 3‐APMo with both substrates in toluene, the second‐order rate coefficients, k_A, show a linear dependence on the [amine]. 3‐APMo is able to form a six‐membered ring by an intramolecular H‐bond which prevents the formation of self‐aggregates. In contrast, a third order was observed in the reactions with 2‐AEPip: these results can be interpreted as a H‐bonded homo‐aggregate of the amine acting as a better nucleophile than the monomer. Most of these results can be well explained within the frame of the ‘dimer nucleophile’ mechanism. Copyright © 2010 John Wiley & Sons, Ltd.     

A Generalization of Stenger’s Lemma to Maximal Dissipative Operators

It is shown that for any maximal dissipative operator A in some Hilbert space \({\mathcal H}\) , which is the orthogonal sum \({\mathcal H=\mathcal F\oplus \mathcal G}\) of two Hilbert spaces \({\mathcal F,\, \mathcal G}\) with \({{\rm dim}\,\mathcal G < \infty}\) , the compression \({\left. T:=P_\mathcal F\,A\right|_{{\rm dom}\,A\cap\mathcal F}}\) of A to \({\mathcal F}\) is again a maximal dissipative operator in \({\mathcal F}\) .     

Isothermal titration calorimetry as a new tool to investigate chiral interactions at crystal surfaces

In this communication we describe for the first time the use of isothermal titration calorimetry (ITC) to measure the energetics of adsorption of enantiomers from aqueous onto chiral crystal surfaces. Our results demonstrate that ITC can be used to measure chiral interactions at crystal surfaces.     

Secondary electron emission control in X-ray photoelectron spectroscopy

Secondary electron emission (SEE) is a major player in surface charging during X-ray photoelectron spectroscopy (XPS); its characteristics and applicability as a current source for electrical measurements are studied. We employ sample biasing and a top retarding grid to control the photoelectron current, and further compare their I–V characteristics with direct spectroscopy of the secondary electrons. Using silica-coated gold substrates, the effect of sample work function on the emitted secondary electrons is shown and fine control over the surface potential gradients, in the range of 10–100 meV, is achieved. XPS-based chemically resolved electrical measurements (CREM) can thus be extended to the positive current regime.     

Energy level and band alignment for GaAs-alkylthiol monolayer-Hg junctions from electrical transport and photoemission experiments

A series of p- and n-GaAs-S-C(n)H(2n+1) || Hg junctions are prepared, and the electronic transport through them is measured. From current-voltage measurements, we find that, for n-GaAs, transport occurs by both thermionic emission and tunneling, with the former dominating at low forward bias and the latter dominating at higher forward bias. For p-GaAs, tunneling dominates at all bias voltages. By combining the analysis of the transport data with results from direct and inverse photoemission spectroscopy, we deduce an energy band diagram of the system, including the tunnel barrier and, with this barrier and within the Simmons tunneling model, extract an effective mass value of 1.5-1.6m(e) for the electronic carriers that cross the junctions. We find that transport is well-described by lowest unoccupied and highest occupied states at 1.3-1.4 eV above and 2.0-2.2 eV below the Fermi level. At the same time, the photoemission data indicate that there are continua of states from the conduction band minimum and the valence band maximum, the density of which varies with energy. On the basis of our results, it appears likely that, for both types of junctions, electrons are the main carrier type, although holes may contribute significantly to the transport in the p-GaAs system.